Bis phenyl (2 carboxylic acid or ester indol-3-yl)methanes

ABSTRACT

The invention provides processes for the preparation of both known and novel [bis(substituted-aryl) (indolyl)]methanes and [(substituted-aryl) (heteryl) (indolyl)]methanes, useful as color formers, particularly in carbonless duplicating and thermal marking systems, which comprises the interaction of [bis(substituted-aryl) (phenylsulfonyl)]methanes and [(substituted-aryl) (heteryl) (phenylsulfonyl)]methanes with indoles in the presence of either an alkaline or an acidic catalyst.

CROSS REFERENCE TO RELATED APPLICATION

This application is a division of our copending application Ser. No.290,657 filed Aug. 6, 1981, and now U.S. Pat. No. 4,403,791.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

This invention relates to a novel process for the preparation of[bis(substituted aryl)(indolyl)]methanes and [(substitutedaryl)(heteryl)(indolyl)methanes useful in the art of carbonlessduplicating as, for example, in pressure-sensitive systems and inthermal marking systems; and to novel [(aryl)(disubstitutedaminoaryl)(indolyl)]methanes, [(aryl)(disubstituted aminoaryl)(indolylcarboxylic acid)]methanes and [(aryl)(julolidino)(indolyl)]methanesproduced by said process.

(b) Description of the Prior Art

Several classes of organic compounds of widely diverse structural typesare known to be useful as colorless precursors for carbonlessduplicating systems. Among the more important classes, there may benamed phenothiazines, for example, benzoyl leuco methylene blue;phthalides, for example, crystal violet lactone; fluorans, for example,2'-anilino-6'-diethylaminofluoran and2'-dibenzylamino-6'-diethylaminofluoran; arylsulfinate salts ofMichler's Hydrol; and various other types of colorless precursorscurrently employed in commercially-accepted carbonless copy systems.Typical of the many such systems taught in the prior art are thosedescribed in U.S. Pat. Nos. 2,712,507, 2,800,457, 3,041,289 and4,000,087, which issued July 5, 1955, July 23, 1957, June 26, 1962 andDec. 28, 1976, respectively. Many of the color formers in the prior artsuffer one or more disadvantages such as low tinctorial strength, poorlight stability, low resistance to sublimation, low susceptibility tocopiability of the color-developed form in standard office copyingmachines, for example, a xerographic type of copier, and low solubilityin common organic solvents, the latter disadvantage thus requiring theuse of specialized and expensive solvents in order to obtainmicroencapsulated solutions of sufficient concentration for use inpressure-sensitive copying systems.

In the prior art, benzoyl leuco methylene blue, related derivatives ofphenothiazines, and analogous compounds derived from phenothiazines havebeen used as slow developing color formers for use in carbonlessduplicating systems in combination with additional art recognizedinstant color-forming compounds.

One of the oldest combinations of color-forming compounds used inpressure-sensitive systems is a mixture of crystal violet lactone andbenzoyl leuco methylene blue. The crystal violet lactone is responsiblefor providing the initial image which is, however, very unstable tolight and moisture. These deficiencies are overcome by the use ofbenzoyl leuco methylene blue which develops slowly upon exposure to air,providing a green-blue image to augment or replace that of the fadingcrystal violet lactone. The developed image of the benzoyl leucomethylene blue is extremely light stable, but is rather green in shade,is lacking in contrast quality, and therefore is unsatisfactory whenmultiple copies are required. Further, it does not possess adequatexerographic copiability on the commercially-available reproductionmachines.

The following items to date appear to constitute the most relevant priorart with regard to the instant invention.

U.S. Pat. No. 3,637,748, issued Jan. 25, 1972, discloses and claims aheteryl methane compound which is free of sulphonic acid groups and hasthe formula ##STR1## wherein R₁ is hydrogen or methyl; R₂ is methyl orphenyl; B stands for a member selected from the group consisting ofphenyl, nitrophenyl, chlorophenyl, dichlorophenyl, methoxyphenyl,methylphenyl, hydroxyphenyl, thienyl-2, and furyl-2; D stands for amember selected from the group consisting of4-methylquinolinyl-methosulphate, 1,2,3,3-tetramethyldihydroindolyl,1-phenyl-3-methylpyrazolone-(5)-yl,1-phenyl-2,3-dimethyl-pyrazolone-(5)-yl, substituted naphthyl,substituted phenyl, substituted chlorophenyl, substituted methylphenyl,substituted hydroxyphenyl and substituted ethoxyphenyl, wherein thesubstituent is located in the 4-position relative to the position atwhich the CH-group is bound and is a member selected from the groupconsisting of phenylamino, ethoxyphenyl, amino, methylphenylamino,methylethoxyphenylamino, piperidino, morpholino, mono-alkylamino whereinthe alkyl portion contains 1-4 carbon atoms, di-lower alkylamino whereinthe lower alkyl portion contains 1-2 carbon atoms, and saidmono-alkylamino and said di-lower alkylamino substituted by a member ofthe group consisting of hydroxy, chloro, cyano and dimethylamino. Theheteryl methane compounds are disclosed as being valuable dyestuffintermediates.

U.S. Pat. No. 3,642,823, issued Feb. 15, 1972, discloses and claims anaminodiphenyl-indolyl-methane dyestuff free of sulfonic acid andcarboxylic acid groups having the formula ##STR2## wherein R ishydrogen, lower alkyl containing 1-5 carbon atoms, nitro, cyano, benzyl,phenyl, carboxylic acid methyl esters, carboxylic acid ethyl ester,unsubstituted carbonamido, substituted carbonamido containingN-substituents selected from the group consisting of lower alkyl, andlower alkyl substituted with Cl, Br, or OH, methylsulfonyl,ethylsulfonyl, phenylsulfonyl, p-toluene sulfonyl, benzoyl, or acetyl;R₁ and R₂ are both hydrogen; or R₁ is unsubstituted lower alkylcontaining 1-5 carbon atoms, substituted lower alkyl containing 1-5carbon atoms and substituted with Cl, Br or OH, benzyl, naphthyl, phenylor phenyl substituted with Cl, Br, lower alkyl or lower alkoxy and R₂ isunsubstituted lower alkyl containing 1-5 carbon atoms, substituted loweralkyl containing 1-5 carbon atoms and substituted with Cl, Br, OH, or CNor benzyl; R₃ is hydrogen, lower alkyl containing 1-5 carbon atoms,lower alkoxy, phenyl, phenyl substituted with chlorine, bromine, loweralkyl or lower alkoxy or carboxylic acid methyl or ethyl ester; R₄ ishydrogen, lower alkyl containing 1-5 carbon atoms, lower alkylcontaining 1-5 carbon atoms substituted with CN, or benzyl; K, L and Mare independently selected from the group consisting of hydrogen, loweralkyl, lower alkoxy, nitro, Cl, and Br, or two of the substituents M arefused to form a naphthalene nucleus; p, q and r are 1 or 2; and X is asubstantially colorless anion which does not impair the solubility ofthe dyestuff in an undesirable manner. The aminodiphenyl-indolyl-methanedyestuffs are described as being useful in the dyeing and printing ofmaterials of leather, tannin-treated cotton, cellulose acetate,synthetic superpolyamides and superurethanes as well as for the dyeingof lignin-containing fibres, such as coconut fibres, jute and sisal.They are also suitable for the production of liquid writing inks,stamping inks, ball point pen pastes and they may also be used in offsetprinting. Above all they are eminently suitable for the dyeing andprinting of materials which are composed partially or completely ofpolymerized acrylonitrile and/or vinylidene cyanide or which arecomposed partially or completely of acid-modified aromatic polyesters,such as sulphonic acid group-containing polyethylene terephthalate.

U.S. Pat. No. 3,995,088, issued Nov. 30, 1976, discloses and claims apressure-sensitive recording material comprising at least one pair ofpaper sheets containing at least two color formers, dissolved in anorganic solvent, and an electron-accepting substance wherein at leastone color former is a leuco methylene dyestuff of the formula ##STR3##wherein Y represents an amino-substituted phenyl residue of the formula##STR4## or an indolyl residue of the formula ##STR5## wherein R₁ andR₂, independently of the other represent hydrogen, alkyl with 1-12carbon atoms, alkoxyalkyl with 2-8 carbon atoms, benzyl or phenyl; R₃ ishydrogen, halogen, nitro, alkyl having 1-4 carbon atoms or alkoxy having1-4 carbon atoms; X₁ represents hydrogen, alkyl with 1-12 carbon atoms,alkenyl with at most 12 carbon atoms or benzyl; X₂ represents hydrogen,alkyl with 1-12 carbon atoms or phenyl; the ring A is unsubstituted orsubstituted by cyano, nitro, halogen, alkyl having 1-4 carbon atoms,alkoxy having 1-4 carbon atoms or acyl with 1-8 carbon atoms; and Zrepresents alkyl with 1-12 carbon atoms, alkenyl with at most 12 carbonatoms, aryl, aralkyl, a heterocyclic radical or the residue of anorganic, particularly aliphatic or cycloaliphatic, compound having aketomethylene group. The other color former is selected from the groupconsisting of crystal violet lactone, benzoyl leuco methylene blue,diamino substituted fluoran compounds, 3-phenyl-3-indolylphthalides or3,3-bis-indolylphthalides or their mixtures thereof.

Whitehead and Whitesilt in the Journal of Medicinal Chemistry 1974 Vol.17, No. 12, 1298-1304 (1974) describe the preparation and physicalcharacteristics of [bis(phenyl)(2-carboxyindol-3-yl)]methane from theinteraction of 2-carboxyindole and benzhydrol in glacial acetic acid.The compound and similar compounds were screened for antimicrobialactivity. Toxicity, behavioral effects, antiviral activity,antiinflammatory properties, antispasmatic activity and generalendocrine properties of the (diarylmethyl)indoles are described.

(c) Prior Publication

West German Offenlegungsschrift No. 2,917,271, which was published onNov. 6, 1980, describes pressure- and heat-sensitive copy material,characterized by the fact that it contains a color component of theformula ##STR6## in which R¹ designates hydrogen, hydroxy, C₁ to C₆alkoxy, C₂ to C₆ alkenyloxy, cycloheyloxy, cyclopentyloxy, possiblybenzyloxy, phenylethyloxy, phenyloxy, naphthyloxy, phenylthio ornaphthylthio, C₁ to C₆ alkylthio substituted by C₁ to C₄ alkyl, C₁ to C₄alkoxy or halogen; R² and R³ independently of one another designatehydrogen, or C₁ to C₆ alkyl possibly substituted by C₁ to C₄ alkoxy, C₁to C₄ alkyl, carbonyloxy, hydroxy, halo or cyano, or benzyl,phenylethyl, phenyl or naphthyl, cyclopentyl or cyclohexyl, substitutedby C₁ to C₄ alkyl, C₁ to C₄ alkoxy or halogen, or R² and R³ along withthe nitrogen atom designate as pyrrolidine, pyrazoline, piperidine ormorpholine ring, or R² along with the nitrogen atom and the ring Bdesignate an indoline or tetrahydroquinoline ring, wherein the ringsmentioned can be substituted by methyl or phenyl; R⁴ designates C₁ to C₄alkyl or phenyl; R⁵ designates hydrogen, possibly C₁ to C₂₂ alkyl, C₂ toC₄ alkenyl, cyclohexyl substituted by cyano, chloro or hydroxy, phenylor benzyl substituted by methyl, ethyl, methoxy, ethoxy or chlorine; R⁶,R⁷ and R⁸ independently of one another designate hydrogen, methyl,ethyl, methoxy, ethoxy or chlorine. This reference appeared subsequentto applicants' invention described herein and less than one year priorto the filing date of this application.

SUMMARY OF THE INVENTION

In its process aspect, the invention relates to the process forproducing a [(X)(Y)(indolyl)]methane which comprises interacting a[(X)(Y)(R-phenylsulfonyl)]methane with an indole.

In one of its composition of matter aspects, the invention relates tocertain [(2-R¹ -3-R² -4-R^(3') -phenyl)(2-R⁴ -4-R⁵ -phenyl)(1-R^(9')-2-R¹⁰ -5/6-R¹¹ -indol-3-yl)]methanes useful as colorless precursors incarbonless duplicating systems.

In a second composition of matter aspect, the invention relates tocertain [(2-R¹ -3-R² -4-R³ -phenyl)(2-R⁴ -4-R⁵ -phenyl)(1-R⁹-2-B"O-carbonyl-5/6-R¹¹ -indol-3-yl)]methanes useful as colorlessprecursors in carbonless duplicating systems.

In a third composition of matter aspect, the invention relates tocertain [(2-R¹ -3-R² -4-R³ -phenyl)(9-julolidinyl)(1-R⁹ -2-R¹⁰ -5/6-R¹¹-indol-3-yl)]methanes useful as colorless precursors in carbonlessduplicating systems.

DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS

More specifically, this invention in one of its process aspects residesin the novel process for the preparation of methanes, which areparticularly useful as colorless precursors in the art of carbonlessduplicating and thermal marking, and provides for the preparation of[(X)(Y)(1-R⁹ -2-R¹⁰ -5/6-R¹¹ -indol-3-yl)]methanes having the formula##STR7## which comprises interacting a[(X)(Y)(R-phenylsulfonyl)]-methane having the formula ##STR8## with anindole of the formula ##STR9## in the presence of an alkaline or an acidcatalyst wherein: X represents a moiety selected from the class havingthe formulas ##STR10## in which R¹ represents hydrogen, C₁ to C₃ alkyl,non-tertiary C₁ to C₄ alkoxy, halo or dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl, R² represents hydrogen or nitro, and R³represents hydrogen, C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo,nitro, dialkylamino or N-alkylbenzylamino in which alkyl is non-tertiaryC₁ to C₄ alkyl and benzyl may be substituted in the benzene ring by oneor two of halo or C₁ to C₃ alkyl; Y represents a moiety selected fromthe group having the formulas ##STR11## in which: R⁴ representshydrogen, C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo ordialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl; R⁵represents hydrogen, C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo,dialkylamino or N-alkylbenzylamino in which alkyl is non-tertiary C₁ toC₄ alkyl and benzyl may be substituted in the benzene ring by one or twoof halo or C₁ to C₃ alkyl; R⁶ represents hydrogen, non-tertiary C₁ toC₁₈ alkyl, C₂ to C₄ alkenyl, benzyl or benzyl substituted in the benzenering by one or two of C₁ to C₃ alkyl or halo; R⁷ represents hydrogen, C₁to C₃ alkyl or phenyl; and R⁸ represents one or two of hydrogen, C₁ toC₃ alkyl, C₁ to C₃ alkoxy, halo or nitro; R⁹ represents hydrogen,non-tertiary C₁ to C₁₈ alkyl, C₂ to C₄ alkenyl, benzyl or benzylsubstituted in the benzene ring by one or two of halo or C₁ to C₃ alkyl;R¹⁰ represents hydrogen, C₁ to C₃ alkyl, phenyl or carboxy; R representsone or two of hydrogen, non-tertiary C₁ to C₁₂ alkyl, C₁ to C₃ alkoxy,halo, nitro or acetamido.

In a first particular embodiment in accordance with its first processaspect, the invention sought to be patented resides in the novel processfor preparing a [(2-R¹ -3-R² -4-R³ -phenyl)(2-R⁴ -4-R⁵ -phenyl)(1-R⁹-2-R¹⁰ -5/6-R¹¹ -indol-3-yl)]methane having the formula ##STR12##wherein R¹, R², R³, R⁴, R⁵, R⁹, R¹⁰ and R¹¹ each have the samerespective meanings given in Formula I.

In a second particular embodiment in accordance with its first processaspect, the invention sought to be patented resides in the novel processfor preparing a [(2-R¹ -3-R² -4-R³ -phenyl)(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)(1-R⁹ -2-R¹⁰ -5/6-R¹¹ -indol-3-yl)]methane having theformula ##STR13## wherein R¹, R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ eachhave the same respective meanings given in Formula I.

In a third particular embodiment in accordance with its first processaspect, the invention sought to be patented resides in the novel processfor preparing a [(2-R¹ -3-R² -4-R³ -phenyl)(9-julolidinyl)(1-R⁹ -2-R¹⁰-5/6-R¹¹ -indol-3-yl)]methane having the formula ##STR14## wherein R¹,R², R³, R⁹, R¹⁰ and R¹¹ each have the same respective meanings given inFormula I.

In a fourth particular embodiment in accordance with its first processaspect, the invention sought to be patented resides in the novel processfor preparing a [(2-thienyl)(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)(1-R⁹ -2-R¹⁰-5/6-R¹¹ -indol-3-yl)]methane having the formula ##STR15## wherein R⁶,R⁷, R⁸, R⁹, R¹⁰ and R¹¹ each have the same respective meanings given inFormula I.

This invention, in its second process aspect, resides in the process forpreparing a [(X)(Y)(1-R⁹ -2-B'O-carbonyl-5/6-R¹¹ -indol-3-yl)]methanehaving the formula ##STR16## which comprises esterifying thecorresponding [(X)(Y)(1-R⁹ -2-carboxy-5/6-R¹¹ -indol-3-)]methane with anappropriate compound selected from the group consisting ofdimethylsulfate, diethylsulfate or B'-halogen in the presence of analkali metal hydroxide or carbonate wherein: X represents a moietyselected from the group having the formulas ##STR17## in which R¹represents hydrogen, C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, haloor dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl; R²represents hydrogen or nitro; and R³ represents hydrogen, C₁ to C₃alkyl, non-tertiary C₁ to C₄ alkoxy, halo, nitro, dialkylamino orN-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄ alkyl andbenzyl is substituted in the benzene ring by one or two of halo or C₁ toC₃ alkyl; Y represents a moiety selected from the group having theformulas ##STR18## in which R⁴ represents hydrogen, C₁ to C₃ alkyl,non-tertiary C₁ to C₄ alkoxy, halo or dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl; R⁵ represents hydrogen, C₁ to C₃ alkyl,non-tertiary C₁ to C₄ alkoxy, halo, dialkylamino or N-alkylbenzylaminoin which alkyl is non-tertiary C₁ to C₄ alkyl and benzyl may besubstituted in the benzene ring by one or two of halo or C₁ to C₃ alkyl;R⁶ represents hydrogen, non-tertiary C₁ to C₁₈ alkyl, C₂ to C₄ alkenyl,benzyl or benzyl substituted in the benzene ring by one or two of C₁ toC₃ alkyl or halo; R⁷ represents hydrogen, C₁ to C₃ alkyl or phenyl; R⁸represents one or two of hydrogen, C₁ to C₃ alkyl, C₁ to C₃ alkoxy, haloor nitro; R⁹ represents hydrogen, non-tertiary C₁ to C₁₈ alkyl, C₂ to C₄alkenyl, benzyl or benzyl substituted in the benzene ring by one or twoof halo or C₁ to C₃ alkyl; R¹¹ represents one or two of hydrogen, C₁ toC₃ alkyl, C₁ to C₃ alkoxy, halo or nitro; and B' represents non-tertiaryC₁ to C₁₈ alkyl, C₂ to C₈ alkenyl, benzyl or benzyl substituted in thebenzene ring by one or two of halo or C₁ to C₃ alkyl.

In a particular embodiment in accordance with its second process aspect,the invention sought to be patented resides in the novel process forpreparing a [(2-R¹ -3-R² -4-R³ -phenyl) (2-R⁴ -4-R⁵ -phenyl) (1-R⁹-2-B'O-carbonyl-5/6-R¹¹ -indol-3-yl)]methane having the formula##STR19## wherein R¹, R², R³, R⁴, R⁵, R⁹, R¹¹ and B' each have the samerespective meanings given in Formula VIII.

This invention, in the first of its composition of matter aspects,resides in the novel methanes, which are particularly useful ascolorless precursors in the art of carbonless duplicating and thermalmarking, and which are [(2-R¹ -3-R² -4-R^(3') -phenyl) (2-R⁴ -4-R⁵-phenyl) (1-R^(9') -2-R¹⁰ -5/6-R¹¹ -indol-3-yl)]methanes having theformula ##STR20## wherein R¹ represents hydrogen, C₁ to C₃ alkyl,non-tertiary C₁ to C₄ alkoxy, halo or dialkylthio in which alkyl isnon-tertiary C₁ to C₄ alkyl; R² represents hydrogen or nitro; R^(3')represents hydrogen, C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo,nitro or when R⁵ is N-alkylbenzylamino, R^(3') further representsdialkylamino or N-alkylbenzylamino in which alkyl is non-tertiary C₁ toC₄ alkyl and benzyl may be substituted in the benzene ring by one or twoof halo or C₁ to C₃ alkyl; R⁴ represents hydrogen, C₁ to C₃ alkyl,non-tertiary C₁ to C₄ alkoxy, halo or dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl; R⁵ represents dialkylamino orN-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄ alkyl andbenzyl may be substituted in the benzene ring by one or two of halo orC₁ to C₃ alkyl; R^(9') represents C₂ to C₁₈ alkyl, C₂ to C₄ alkenyl,benzyl or benzyl substituted in the benzene ring by one or two of haloor C₁ to C₃ ; R¹⁰ represents hydrogen, C₁ to C₃ alkyl or phenyl; and R¹¹represents one or two of hydrogen, C₁ to C₃ alkyl, C₁ to C₃ alkoxy, haloor nitro.

This invention, in its second composition of matter aspect, resides inthe novel methanes, which are particularly useful as colorlessprecursors in the art of carbonless duplicating and thermal marking, andwhich are [(2-R¹ -3-R² -4-R³ -phenyl) (2-R⁴ -4-R⁵ -phenyl) (1-R⁹-2-B"O-carbonyl-5/6-R¹¹ -indol-3-yl)]methanes having the formula##STR21## wherein R¹ represents hydrogen, C₁ to C₃ alkyl, non-tertiaryC₁ to C₄ alkoxy, halo or dialkylamino in which alkyl is non-tertiary C₁to C₄ alkyl; R² represents hydrogen or nitro; R³ represents hydrogen, C₁to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo, dialkylamino orN-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄ alkyl andbenzyl may be substituted in the benzene ring by one or two of halo orC₁ to C₃ alkyl; R⁴ represents hydrogen, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy, halo or dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl; R⁵ represents dialkylamino orN-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄ alkyl andbenzyl may be substituted in the benzene ring by one or two of halo orC₁ to C₃ alkyl; R⁹ represents hydrogen, C₁ to C₁₈ alkyl, C₂ to C₄alkenyl, benzyl and benzyl substituted in the benzene ring by one or twoof halo; R¹¹ represents one or two of hydrogen, C₁ to C₃ alkyl, C₁ to C₃alkoxy, halo or nitro; and B" represents hydrogen, C₁ to C₁₈ alkyl, C₂to C₈ alkenyl, benzyl or benzyl substituted in the benzene ring by oneor two of halo or C₁ to C₃ alkyl.

This invention, in its third composition of matter aspect, resides inthe novel methanes, which are particularly useful as colorlessprecursors in the art of carbonless duplicating and thermal marking, andwhich are [(2-R¹ -3-R² -4-R³ -phenyl) (9-julolidinyl)(1-R⁹ -2-R¹⁰-5/6-R¹¹ -indol-3-yl)]methanes having the formula ##STR22## wherein R¹represents hydrogen, C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, haloor dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl; R²represents hydrogen or nitro; R³ represents hydrogen, C₁ to C₃ alkyl,non-tertiary C₁ to C₄ alkoxy, halo, nitro, dialkylamino orN-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄ alkyl andbenzyl may be substituted in the benzene ring by one or two of halo oralkyl; R⁹ represents hydrogen, C₁ to C₁₈ alkyl, C₂ to C₄ alkenyl, benzylor benzyl substituted in the benzene ring by one or two of halo or C₁ toC₃ alkyl; R¹⁰ represents hydrogen, C₁ to C₃ alkyl, phenyl or --COB" inwhich B" represents hydrogen, C₁ to C₁₈ alkyl, C₂ to C₈ alkenyl, benzylor benzyl substituted in the benzene ring by C₁ to C₁₂ alkyl, halo or C₁to C₈ alkoxy; and R¹¹ represents one or two of hydrogen, C₁ to C₃ alkyl,C₁ to C₃ alkoxy, halo or nitro.

In the first of its article of manufacture aspects, the invention soughtto be patented resides in a pressure-sensitive carbonless duplicatingsystem or a thermal marking system containing a support sheet coatedwith a layer containing a color-forming substance comprising a compundhaving the formula ##STR23## wherein R¹ represents hydrogen, C₁ to C₃alkyl, non-tertiary C₁ to C₄ alkoxy, halo or dialkylamino in which alkylis non-tertiary C₁ to C₄ alkyl; R² represents hydrogen or nitro; R^(3')represents hydrogen, C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo,nitro or when R⁵ is N-alkylbenzylamino, R^(3') further representsdialkylamino or N-alkylbenzylamino in which alkyl is non-tertiary C₁ toC₄ alkyl and benzyl may be substituted in the benzene ring by one or twoof halo or C₁ to C₃ alkyl; R⁴ represents hydrogen, non-tertiary C₁ to C₄alkyl, non-tertiary C₁ to C₄ alkoxy, halo or dialkylamino in which alkylis non-tertiary C₁ to C₄ alkyl; R⁵ represents dialkylamino orN-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄ alkyl andbenzyl may be substituted in the benzene ring by one or two of halo orC₁ to C₃ alkyl; R⁹ represents hydrogen, non-tertiary C₁ to C₁₈ alkyl, C₂to C₄ alkenyl, benzyl or benzyl substituted in the benzene ring by oneor two of halo or C₁ to C₃ alkyl; R¹⁰ represents hydrogen, C₁ to C₃alkyl or phenyl; and R¹¹ represents one or two of hydrogen, C₁ to C₃alkyl, C₁ to C₃ alkoxy, halo or nitro.

In a second of its article of manufacture aspects, the invention soughtto be patented resides in a pressure-sensitive carbonless duplicatingsystem or a thermal marking system containing a support sheet coatedwith a layer containing as a color-forming substance a [(2-R¹ -3-R²-4-R³ -phenyl)(2-R⁴ -4-R⁵ -phenyl)(1-R⁹ -2-B"O-carbonyl-5/6-R¹¹-indol-3-yl)]methane according to Formula XI or a [(2-R¹ -3-R² -4-R³-phenyl)(9-julolidinyl)(1-R⁹ -2-R¹⁰ -5/6-R¹¹ -indol-3-yl)]methaneaccording to Formula XII wherein R¹, R², R³, R⁴, R⁵, R⁹, R¹⁰, R¹¹ and B"each have the same respective meanings given in relation to Formula XIor Formula XII.

A particular embodiment sought to be patented in accordance with itsarticle of manufacture aspects resides in a pressure-sensitive transfersheet, adapted for use with a receiving sheet having an electronaccepting layer, comprising a support sheet coated on one side with alayer of pressure-rupturable microcapsules containing a liquid solutionof a color-forming substance comprising at least one compound depictedby Formula XI, by Formula XII or by Formula XIII.

Another particular embodiment sought to be patented in accordance withits article of manufacture aspects resides in a heat responsive recordmaterial comprising a support sheet coated on one side with a layercontaining a mixture comprising at least one color-forming compoundhaving Formula XI, Formula XII or Formula XIII and an acidic developerarranged such that application of heat will produce a mark-formingreaction between the color-forming compound and the acidic developer.

Still another particular embodiment sought to be patented in accordancewith its article of manufacture aspects resides in a heat responsiverecord material comprising a support sheet coated on one side with alayer containing a mixture comprising at least one color-formingcompound having Formula XI, Formula XII or Formula XIII and an oxidizingagent arranged such that application of heat will produce a mark-formingreaction between the color-forming compound and the oxidizing agent.

As used herein the term "halo" includes chloro, fluoro, bromo and iodo.Chloro is the preferred halo substituent because of the relatively lowcost and ease of preparation of the required chloro-substitutedintermediates and because the other halogens offer no particularadvantages over chloro. However, the other above-named halo substituentsare also satisfactory.

The term "dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl"denotes saturated, acyclic groups which may be straight or branched asexemplified by dimethylamino, diethylamino, ethylmethylamino,dipropylamino, dibutylamino, isobutylmethylamino and the like.

The term "N-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄alkyl and benzyl may be substituted in the benzene ring by one or two ofhalo or C₁ to C₃ alkyl" denotes an amino moiety which is substitutedwith an acyclic group which may be straight or branched and one benzylgroup as exemplified by N-methylbenzylamino, N-ethylbenzylamino,N-propylbenzylamino, N-butylbenzylamino,N-ethyl(2,5-dimethylbenzyl)amino, N-ethyl(4-chlorobenzyl)amino and thelike.

As used herein the terms "C₁ to C₃ alkyl", "non-tertiary C₁ to C₄alkyl", "non-tertiary C₁ to C₁₂ alkyl" and "non-tertiary C₁ to C₁₈alkyl" denote saturated monovalent straight or branched aliphatichydrocarbon radicals including methyl, ethyl, propyl, isopropyl, butyl,isobutyl, amyl, 1-methylbutyl, 3-methylbutyl, hexyl, isohexyl, heptyl,isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, 3-ethylheptyl, n-decyl,n-undecyl, n-dodecyl, n-tridecyl, n-octodecyl, 1,3,5-trimethylhexyl,1,5-dimethyl-4-ethylhexyl, 5-methyl-2-butyl-hexyl, 2-propylnonyl,2-butyloctyl, 2-pentanonyl, 1,2-dimethylhexadecyl and the like.

The terms "C₁ to C₃ alkoxy" and "non-tertiary C₁ to C₄ alkoxy" includesaturated acyclic, straight or branched-chained groups such as methoxy,ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, and isobutoxy.

As used herein, the terms "C₂ to C₄ alkenyl" and "C₂ to C₈ alkenyl" meanmonovalent aliphatic radicals possessing a single double bond, forexample, ethenyl (or vinyl), 2-propenyl (or allyl), 1-methylethenyl (orisopropenyl), 2-methyl-2-propenyl, 2-methyl-1-propenyl, 2-butenyl,3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-2-butenyl,2-methyl-1-butenyl (isoamylenyl), 3-methyl-1-butenyl, 1-hexenyl,2-hexenyl, 3-hexenyl, 2-heptenyl and 1-octenyl.

As used herein, the term "acid catalyst" denotes any material which isacidic in nature. Among these catalysts are acidic halide Lewis acidcatalysts, Bronsted acid catalysts, acidic oxide catalysts, acidiccation exchange resin catalysts, and any organic or inorganic materialwhich is capable of partial hydrolysis in the reaction medium to formacidic conditions. Examples of catalysts are hydrobromic acid,hydrochloric cid, hydriodic acid, sulfuric acid, phosphoric acid, nitricacid, fluoroboric acid, perchloric acid, arylsulfonic acids andalkylsulfonic acids, for example, p-toluenesulfonic acid,methanesulfonic acid, formic acid, acetic acid, glycolic acid, lacticacid, propionic acid, monochloroacetic acid, dichloroacetic acid,trichloroacetic acid, trifluoroacetic acid, malonic acid, citric acid,fumaric acid, benzoic acid, salicylic acid, picric acid, trimelliticacid, aluminum chloride, ferric chloride, zinc chloride, stannicchoride, phosphorus trichloride, phosphorus pentachloride, borontrifluoride etherate, phosphorous oxychloride, thionyl chloride, ferricoxide, aluminum oxide, phosphorus pentaoxide, benzoyl chloride, benzoylperoxide, potassium fluoride, sulfonated coals, sulfonatedphenol-formaldehyde resins, sulfonated divinylbenzene cross linkedpolymers and exchangers with carboxyl group, phenol group oralumina-silicate skeleton.

As used herein the term "alkaline catalyst" is intended to be inclusiveof both inorganic and organic basic compounds. Among these catalysts aresodium hydroxide, potassium hydroxide, lithium hydroxide, sodiumcarbonate, potassium carbonate, lithium carbonate, ammonium hydroxide,tetramethylammonium hydroxide, tetraethylammonium hydroxide,tetrabutylammonium hydroxide, quinuclidine,1,4-diazobicyclo[2,2,2]-octane, triethanolamine, triethylamine and urea.

As used herein the term "reaction medium" denotes any non-solvent orsolvent capable of dispersing, partially dissolving or completelydissolving the reactants thus providing a fluid medium for thesereactants to interact forming the desired methanes. Examples of chemicalcompounds which may be utilized singly or in a combination as a"reaction medium" are methyl alcohol, ethyl alcohol, isopropyl alcohol,ethylene glycol, ethylene glycol monoethyl ether, propylene glycol,diethylene glycol, diethylene glycol dimethyl ether, acetonitrile,ethylene dichloride N,N-dimethylformamide, N,N-dimethylaniline,isopropyl crown ether, acetone, ethylmethylketone, propylmethylketone,butylmethylketone and water.

The compounds of Formula I, (which of course encompass the novelcompounds of Formula X, Formula XI and Formula XII) and those of FormulaXIII, hereinabove are essentially colorless in the depicted form. Whencontacted with an acidic medium, for example, silica gel or one of thetypes ordinarily employed in pressure-sensitive carbonless duplicatingsystems such as silton clay or phenolic resins, the compounds of FormulaI develop green-gray, brown, purple, violet, blue-red, red, and gray toblack-colored images in the air or in the presence of an oxidizingagent. These developed images are very insensitive to light, are of goodto excellent tinctorial strength, possess excellent xerographiccopiability and enhanced solubility in common organic solvents. Thecompounds are thus highly suitable for use as colorless precursors, thatis, color-forming substances in pressure-sensitive carbonlessduplicating systems. The darker violet colors can be used alone as colorformers to produce images which are readily copiable, whereas the brown,red and blue colors can be used as toners in admixture with other colorformers to produce images of a neutral shade which desirably are readilycopiable by xerographic means.

The methane compounds of Formulas I, X, XI, XII and XIII are generallyused in admixture with one or more other color formers selected from theclasses consisting of phthalides, for example, crystal violet lactone;fluorans, for example, 2'-anilino-6'-diethylaminofluoran and2'-dibenzylamino-6'-diethylaminofluoran; phenothiazines, for example,benzoyl leuco methylene blue; arylsulfinate salts of Michler's Hydrol;the various other types of colorless precursors currently employed incommercially-accepted carbonless copy systems.

The compounds of this invention may be incorporated in any of thecommercially-accepted systems known in the carbonless duplicating art. Atypical technique for such application is as follows. Solutionscontaining one or more colorless compounds of Formulas I, X, XI, XII andXIII optionally in admixture with other color formers, in suitablesolvent are microencapsulated by well-known procedures, for example, asdescribed in U.S. Pat. Nos. 3,649,649, 3,429,827 and 4,000,087. Themicrocapsules are coated on the reverse side of a sheet with the aid ofa suitable binder and the coated transfer sheet is then assembled in amanifold with the microcapsule coated side in contact with a receivingsheet coated with an electron-accepting substance, for example, siltonclay or a phenolic resin. Application of pressure to the manifold suchas that exerted by a stylus, typewriter or other form of writing orprinting causes the capsules on the reverse side to rupture. Thesolution of the color formers released from the ruptured microcapsulesflows to the receiving sheet and on contact with the acidic mediumthereon forms green-gray to reddish-violet colored images of goodtinctorial strength. It is, of course, obvious that variants of thismode of application can be utilized. For example, the receiving sheet ina manifold can alternatively be coated with the subject compounds andthe acidic developing agent can be contained in microcapsules applied tothe reverse side of the top sheet in the manifold; or the receivingsheet can be coated with a mixture containing both the acidic developingagent and the microencapsulated color former.

It has also been found that when the compounds of Formulas I, X, XI, XIIand XIII are intimately mixed with an acidic developer of the typegenerally employed in thermal papers such as described in U.S. Pat. No.3,539,375, that is, papers which produce a colored image when contactedwith a heated stylus or heated type, for example, bisphenol A, heatingof the mixture produces a colored image of varying shades fromgreen-gray to reddish-violet depending on the particular compound of theinvention employed. The ability of the compounds of Formulas I, X, XI,XII and XIII to form a deep color when heated in admixture with anacidic developer such as bisphenol A, makes them useful in thermal papermarking systems, either where an original or a duplicate copy isprepared by contacting the thermal paper with a heated stylus or heatedtype in any of the methods generally known in the art.

Further, it has been found that when the compounds of Formulas I, X, XI,XII and XIII are intimately mixed with an oxidizing agent developer ofthe type employed in thermal papers such as described in U.S. Pat. No.3,447,994, that is, papers which produce a colored image when contactedwith a heated stylus or heated type, for example, benzoyl peroxide,heating of the mixture produces a colored image of varying shades fromgreen-gray to reddish-violet depending on the particular compound of theinvention employed. The ability of the compounds of Formulas I, X, XI,XII and XIII to form a deep color when heated in admixture, makes themuseful in thermal paper marking systems, either where an original or aduplicate copy is prepared by contacting the thermal paper with a heatedstylus or heated type in any of the methods generally known in the art.

The best mode contemplated by the inventors of carrying out thisinvention will now be described so as to enable any person skilled inthe art to which it pertains to make and use the same.

In accordance with the aforementioned process aspect of this inventionthe [(X)(Y)(indolyl)]methanes of Formula I which encompass both knowntrisubstituted methanes and the novel methanes of Formulas X, XI and XIIare obtained by reacting approximately equimolar amounts of a[(X)(Y)(R-phenylsulfonyl)]methane compound of Formula II and a 1-R⁹-2-R¹⁰ -5/6-R¹¹ -indole of Formula III wherein X, Y, R, R⁹, R¹⁰ and R¹¹have the same respective meanings given above in relation to Formulas I,II and III. These reactions are conveniently carried out in a reactionmedium, for example, a lower hydrocarbon chain alcohol, such as ethanol,or a lower hydrocarbon chain ketone, such as acetone, in the presence ofan alkaline or an acidic catalyst, for example, potassium hydroxide orhydrochloric acid, at a temperature in the range of 0°-100° C. forapproximately one to approximately seventy hours. The[(X)(Y)(indolyl)]methanes of Formula I thus obtained can be isolated byfiltration if the product is not soluble in the reaction medium.Alternatively, the reaction mixture can be poured into water or a diluteaqueous base, for example, ammonium hydroxide and the methane isolatedby filtration or extracted with an organic solvent, for example, toluenefollowed by evaporation of the organic solvent leaving the product as aresidue. The isolated methane can be purified by conventional means suchas trituration, recrystallization or reslurrying with a suitable organicliquid.

In accordance with another of the process aspects of this invention, the[(X)(Y)(1-R⁹ -2-B'O-carbonyl-5/6-R¹¹ -indol-3-yl)]methanes of FormulaVIII wherein X, Y, R⁹, R¹¹ and B' each have the same respective meaningsgiven in relation to Formula VIII are obtained by interacting a[(X)(Y)(1-R⁹ -2-carboxy-5/6-R¹¹ -indol-3-yl)]methane with an appropriatealkylating agent, for example, dimethyl sulfate, diethyl sulfate, ethyliodide, n-butyl bromide, n-hexadecyl bromide, benzyl bromide, benzylchloride, and the like in an inert diluent, for example,N,N-dimethylformamide, acetone, isopropyl alchol and the like in thepresence of an alkali metal hydroxide or carbonate, for example, sodiumhydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.The reaction is conveniently carried out at a temperature in the rangeof 30°-60° C. for approximately one-half to approximately ten hours. Thecorresponding methanes thus obtained are isolated by slowly adding thereaction mixture to a mixture of ice and water. The product whichseparates is then collected by filtration. The methane thus obtained canbe purified, if needed, by conventional means, for example, byreslurrying in, or recrystallizing from an organic liquid.

The [(X)(Y)(R-phenylsulfonyl)]methanes of Formula II required asstarting materials in the preparation of the products of Formula I areknown, for example, as disclosed in U.S. Pat. No. 4,257,954, whichissued on Mar. 24, 1981, in the names of Paul Joseph Schmidt and WilliamMo-Wei Hung. This patent is hereby incorporated by reference.

The indole compounds represented by 1-R⁹ -2-R¹⁰ -5/6-R¹¹ -indole whichare required to obtain the [(X)(Y)(1-R⁹ -2-R¹⁰ -5/6-R¹¹-indol-3-yl)]methanes of Formula I form an old and well-known class ofcompounds readily obtained by conventional processes well known in theart. The following list of compounds exemplifies indole compoundsfalling within the ambit of the 1-R⁹ -2-R¹⁰ -5/6-R¹¹ -indole, which areuseful in the practice of the processes of this invention for producingthe aforesaid methanes of Formula I. Indole, 1-methylindole,2-methylindole, 1,2-dimethylindole, 1-ethyl-2-methylindole,2-phenylindole, 1-propyl-2-methylindole, 1-benzyl-2-methylindole,1-butyl-2-methylindole, 1-octyl-2-methylindole, 2-ethyl-5-methylindole,1-benzyl-5-fluoroindole, 1-methyl-6-nitroindole,5-methoxy-1-butylindole, 1-allyl-2-methylindole,1,2-dimethyl-6-nitroindole, 1-(4-chlorobenzyl)-2-methyl-5-nitroindole,2-ethylindole, 2-ethyl-1-methylindole, 1-isopropylindole,2-isopropylindole, 1-methyl-5-bromo-6-nitroindole,2,5,6-trimethylindole, 1-isobutyl-2-methylindole,6-bromo-2-methylindole, 1-hexylindole,1-(2,5-dimethylbenzyl)-2-methylindole, 2-propylindole,6-chloro-2-phenylindole, 1-(2-ethylhexyl)-2 -methylindole,1-(2,6-dichlorobenzyl)-2-methylindole, 1-vinyl-2-methylindole,2-ethyl-6-methylindole, 6-fluoro-1-benzylindole,1-(4-bromobenzyl)-2-isopropylindole, 1-(3-chlorobenzyl)-2-ethylindole,5-chloro-1-benzylindole, 1-(2-fluorobenzyl)-2-methylindole,5-iodo-1-(1-methylhexyl)indole, 5,6-dimethoxyindole,1-(2-methylbenzyl)-2-methylindole, 5,6-dichloro-2-phenylindole,1-isoamylindole, 1-[3-(2-methyl)-1-propenyl]-2-methoxyindole,indole-2-carboxylic acid, 5-chloroindole-2-carboxylic acid,5-methoxyindole-2-carboxylic acid, 1-methylindole-2-carboxylic acid,1-butylindole-2-carboxylic acid, 1-ethylindole-2-carboxylic acid and1-hexdecylindole-2-carboxylic acid.

The molecular structures of the compounds of this invention wereassigned on the basis of the modes of synthesis and study of theirinfrared and nuclear magnetic resonance spectra.

The following examples will further illustrate the invention without,however, limiting it thereto. All melting points are uncorrected.

EXAMPLE 1

With stirring, 3.0 ml of concentrated hydrochloric acid was added to amixture of 8.0 g of [bis(4-dimethylaminophenyl)(4-methylphenylsulfonyl]methane, 4.0 g of 85 percent1-ethyl-2-methylindole and 150.0 ml of acetone. After stirringapproximately twenty hours at ambient temperature, the resultantsolution was added slowly with stirring to a solution consisting of 25.0ml of concentrated ammonium hydroxide and one liter of water. The solidwhich separated was collected by filtration. The water-wet filter cakewas reslurried in 150.0 ml of ethyl alcohol at reflux temperature forapproximately thirty minutes. After cooling to room temperature, thesolid was collected by filtration and dried to obtain 5.5 g of[bis(4-dimethylaminophenyl) (1-ethyl-2-methylindol-3-yl)]methane(Formula IV: R¹ ═R² ═R⁴ ═R¹¹ ═H; R³ ═R⁵ ═N(CH₃)₂ ; R⁹ ═C₂ H₅ ; R¹⁰═CH₃), a white-colored solid which melted at 165°-166° C. The nuclearmagnetic resonance spectrum was concordant with the assigned structure.An infrared maximum appeared at 740 (C--H;s) cm⁻¹. A toluene solution ofthe product spotted on an acidic clay-coated paper or phenolicresin-coated paper slowly developed a violet-colored image.

EXAMPLE 2

To a stirred mixture{(4-dimethylaminophenyl)[4-(N-ethylbenzylamino)phenyl](4-methylphenylsulfonyl)}methane,1.6 g of 2-methyl-5-methoxyindole and 150.0 ml of acetone, there wasadded 2.0 g of potassium hydroxide. The resultant mixture was stirredapproximately five hours at ambient temperature and then was addedslowly to stirred mixture of water and toluene. After approximatelythirty minutes the stirring was stopped and the water was separated fromthe toluene layer and discarded. The toluene layer was mixed with anaqueous saturated sodium chloride solution, the layers allowed toseparate and the salt water layer separated and discarded. The toluenelayer was then evaporated under ambient conditions to obtain a residuewhich was triturated with a mixture of equal volumes of hexane andisopropyl alcohol. The solid which formed was collected by filtrationand dried to obtain 1.9 g of{(4-dimethylaminophenyl)[4-(N-ethylbenzylamino)phenyl](2-methyl-5-methoxyindol-3-yl)}methane(Formula X: R¹ ═R² ═R⁴ ═R^(9') ═H; R^(3') ═N(CH₃)₂ ; R⁵ ═N(C₂ H)₅ (CH₂C₆ H₅); R¹⁰ ═CH₃ ; R¹¹ ═OCH₃), a light gray-colored solid which meltedat 169°-172° C. A maximum appeared in the infrared spectrum at 740(C--H;s) cm⁻¹. A toluene solution of the product spotted on an acidicclay-coated paper or a phenolic resin-coated paper slowly developed aviolet-colored image.

EXAMPLE 3

With stirring, 2.0 g of potassium hydroxide was added slowly to amixture of 6.7 g of[(4-dimethylaminophenyl)(1-ethyl-2-methylindol-3-yl)(4-methylphenylsulfonyl)]methane,2.5 g of 2-methylindole and 75.0 ml of acetone. The resulting mixturewas stirred approximately twenty hours at ambient temperature and slowlyadded with stirring to cold water. The precipitate which formed wascollected by filtration and washed three times each with 50.0 ml ofhexane. The hexane-wet filter cake was dissolved in toluene. The toluenesolution was extracted with water and the toluene layer containing theproduct was stirred with decolorizing carbon for approximately thirtyminutes and the carbon removed by filtration. The toluene was removed bydistillation at reduced pressure to obtain a gum-like residue. Theresidue was dissolved in 150.0 ml of acetone and the resulting solutionwas added slowly to a mixture of 800.0 ml of water, 10.0 ml ofconcentrated ammonium hydroxide and 50.0 ml of saturated aqueous sodiumchloride solution. The solid which separated was collected byfiltration, washed with water and dried in vacuo to obtain 3.9 g of[(4-dimethylaminophenyl)(1-ethyl-2-methylindol-3-yl)(2-methylindol-3-yl)]methane(Formula V: R¹ ═R² ═R⁸ ═R⁹ ═R¹¹ ═H; R³ ═N(CH₃)₂ ; R⁷ ═R¹⁰ ═CH₃ ; R⁶ ═C₂H₅), a pale brown-colored solid which melted over the range of 69°-80.5°C. An infrared maxima appeared at 745 (C--H;s) cm⁻¹. A toluene solutionof the product spotted on an acidic clay-coated paper or phenolicresin-coated paper slowly developed a blue-red-colored image.

EXAMPLE 4

With stirring, 2.0 g of potassium hydroxide was added slowly to amixture of 6.7 g of[(4-dimethylaminophenyl)(1-ethyl-2-methylindol-3-yl)(4-methylphenylsulfonyl)]methane,2.4 g of indole and 75.0 ml of acetone. The resultant mixture wasstirred approximately 65 hours at ambient temperature. Fifty millilitersof isopropyl alcohol was added to the reaction mixture and the resultingsolution was added slowly to water. The gum-like residue which resultedwas isolated by decanting the supernatant liquid. The residue wastriturated with a mixture of 66.6 ml of hexane and 133.4 ml of isopropylalcohol. The solid which formed was collected by filtration to obtain0.4 g of a brown solid. The filtrate was added to a mixture of tolueneand water. After mixing thoroughly, the layers separated and the waterlayer was removed. The toluene layer was washed first with water andthen with saturated aqueous sodium chloride solution. The resultingtoluene layer was distilled under reduced pressure to obtain a gum-likeresidue which was triturated with hexane. The solid which formed wascollected by filtration and dried to obtain 3.6 g of[(4-dimethylaminophenyl)(1-ethyl-2-methylindol-3-yl)(indol-3-yl)]methane(Formula V: R¹ ═R² ═R⁸ ═R⁹ ═R¹⁰ ═R¹¹ ═H; R³ ═N(CH₃)₂ ; R⁶ ═C₂ H₅ ; R⁷═CH₃), a pale brown-colored solid which melted over the range 142°-151°C. The infrared spectrum of the product had a significant maximum at 745(C--H;s) cm⁻¹. A toluene solution of the product spotted on an acidicclay-coated paper or a phenolic resin-coated paper slowly developed ared-colored image.

EXAMPLE 5

To a mixture of 4.1 g of[(2-thienyl)(1-ethyl-2-methylindol-3-yl)(4-methylphenylsulfonyl)]methane,2.0 g of 2-methylindole and 70.0 ml of acetone, there was added slowly2.0 g of potassium hydroxide. The resulting solution was stirredapproximately twenty hours at ambient temperature. The solid whichformed was collected by filtration, washed with a small amount ofacetone, then washed alkali-free with water and dried to obtain 1.2 g of[(2-thienyl)(1-ethyl-2-methylindol-3-yl)(2-methylindol-3-yl)]methane(Formula VII: R⁶ ═C₂ H₅ ; R⁷ ═R¹⁰ ═CH₃ ; R⁸ ═R⁹ ═R¹¹ ═H), awhite-colored solid which melted at 177°-179° C. The infrared spectrumhad a significant maximum at 750 (C--H;s) cm⁻¹. The nuclear magneticresonance spectrum was consistent with the assigned structure. A toluenesolution of the product spotted on an acid clay-coated paper or aphenolic resin-coated paper slowly developed a chocolate brown-coloredimage.

EXAMPLE 6

Two grams of potassium hydroxide was added slowly to a mixture of 6.3 gof [bis(4-dimethylaminophenyl)(4-methylphenylsulfonyl)]methane, 2.5 g of2-methylindole and 75.0 ml of acetone. The resulting slurry was stirredfor approximately 24 hours at ambient temperature. Fifty milliliters ofisopropyl alcohol was added to the reaction mixture to effect completesolution. Slowly with stirring, the resulting solution was added to oneliter of water and the solid which formed was collected by filtration.The wet filter cake was suspended in 100.0 ml of isopropyl alcohol andstirred approximately thirty minutes. The solid was collected byfiltration, washed twice with 25.0 ml of isopropyl alcohol each anddried to obtain 5.1 g of[bis(4-dimethylaminophenyl)(2-methylindol-3-yl)]methane (Formula IV: R¹═R² ═R⁴ ═R⁹ ═R¹¹ ═H; R³ ═R⁵ ═N(CH₃)₂ ; R¹⁰ ═CH₃), a pale gray-coloredsolid which melted at 198°-202° C. A significant infrared maximumappeared at 740 (C--H;s) cm⁻¹. The nuclear magnetic resonance spectrumwas concordant with the assigned structure. A toluene solution of theproduct spotted on an acid clay-coated paper or a phenolic resin-coatedpaper slowly developed a grape-colored image.

The following table (Table A) lists [(X)(Y)(1-R⁹ -2-R¹⁰ -5/6-R¹¹-indol-3-yl)]methanes prepared from the interaction of a[(X)(Y)(R-phenylsulfonyl)]methane and a 1-R⁹ -2-R¹⁰ -5/6-R¹¹ -indole inthe presence of an acid or an alkaline catalyst in a manner similar tothat described in Examples 1-6 above. The starting methanes listed inthe second column were interacted with the indoles shown in the thirdcolumn in the presence of a catalyst indicated in the fourth column inthe reaction medium designated in the fifth column. The substitutedmethane product, obtained is listed in the sixth column with its formulanumber and substitutents so indicated in the seventh and eighth columns,respectively and the product's appearance and melting point in the ninthand tenth columns, respectively. A significant infrared maximum is shownin the eleventh column and the results of the nuclear magnetic spectralanalysis are shown in the twelth column. The substituted methanes weretested as carbonless duplicating color precursors by dissolving theproduct in toluene and streaking the toluene solution on an acidicclay-coated paper sheet and a phenolic resin-coated paper sheet. Thecolors of the images which slowly developed in this streaking test areindicated in the thirteenth column of the table. Table A has beendivided into two parts, Part I contains Columns 1 through 6 and Part IIcontains Columns 7 through 13.

                                      TABLE A                                     __________________________________________________________________________    PART I                                                                        Example  Starting                    Reaction  Methane                        No.      Material    Indole     Catalyst                                                                           Medium    Product                        __________________________________________________________________________     7   7.5 g                                                                             [Bis(4-dimethyl-                                                                          2.4 g                                                                             Indole KOH  Acetone                                                                             4.8 g                                                                             [Bis(4-dimethylamino-                   aminophenyl)(4-                       phenyl)(indol-3-yl)]-                   methylphenylsul-                      methane                                 fonyl)]methane                                                        8   8.0 g                                                                             [Bis(4-dimethyl-                                                                          3.5 g                                                                             2-Methyl-                                                                            HCl  Acetone                                                                             6.2 g                                                                             [Bis(4-dimethylamino-                   aminophenyl)(4- indole                phenyl)(2-methylindol-                  methylphenylsul-                      3-yl)]methane                           fonyl)]methane                                                        9   5.0 g                                                                             [(4-Dimethylamino-                                                                        2.0 g                                                                             2-Meth-                                                                              KOH  Acetone                                                                             3.6 g                                                                             [(4-Dimethylaminophen-                  phenyl)(4-N--ethyl-                                                                           ylindole              yl)(4-N--ethylbenzyl-                   benzylaminophenyl)]-                  aminophenyl)(2-methyl-                  methane                               indol-3-yl)]methane            10   5.0 g                                                                             [(4-Dimethylamino-                                                                        1.7 g                                                                             1-Ethyl-                                                                             HCl  Ethanol                                                                             3.1 g                                                                             [(4-Dimethylaminophen-                  phenyl)(4-N--ethyl-                                                                           2-methyl-             yl)(4-N--ethylbenzyl-                   benzylaminophenyl)                                                                            indole                aminophenyl)(1-ethyl-2-                 (4-methylphenyl-                      methylindol-3-yl)]-                     sulfonyl)]methane                     methane                        11   8.0 g                                                                             [Bis(4-dimethyl-                                                                          3.1 g                                                                             1,2-Di-                                                                              HCl  Ethanol                                                                             8.0 g                                                                             [Bis(4-dimethylamino-                   aminophenyl)(4- methyl-               phenyl)(1,2-dimethyl-                   methylphenylsulfon-                                                                           indole                indol-3-yl)]methane                     yl)]methane                                                          12   8.0 g                                                                             [Bis(4-dimethyl-                                                                          4.97 g                                                                            1- -n-butyl-                                                                         HCl  Ethanol                                                                             10.3 g                                                                            [Bis(4-dimethylamino-                   aminophenyl)(4- 2-methyl-             phenyl)(1- -n-butyl-2-                  methylphenylsul-                                                                              indole                methylindol-3-yl)]-                     fonyl)methane                         methane                        13   5.0 g                                                                             [(4-Dimethyl-                                                                             1.6 g                                                                             1,2-Dimeth-                                                                          HCl  Ethanol                                                                             4.9 g                                                                             [(4-Dimethylaminophenyl)                aminophenyl)(4- ylindole              (4-N--ethylbenzylamino-                 N--ethylbenzyl-                       phenyl)(1,2-dimethylindol-                                                    9                                       aminophenyl)(4-                       3-yl)]methane                           methylphenylsul-                                                              fonyl)]methane                                                       14   5.0 g                                                                             [(4-Dimethyl-                                                                             1.2 g                                                                             Indole KOH  Acetone                                                                             1.2 g                                                                             [(4-Dimethylaminophenyl)                aminophenyl)(4-                       (4-N--ethylbenzylamino-                 N--ethylbenzyl-                       phenyl)(indol-3-yl]methane                                                    .                                       aminophenyl)(4-                                                               methylphenylsul-                                                              fonyl)]methane                                                       15   4.7 g                                                                             [4-Methoxyphenyl)                                                                         1.6 g                                                                             1,2-Dimeth-                                                                          HCl  Ethanol                                                                             1.9 g                                                                             [(4-Methoxyphenyl)(2-                   (2-ethoxy-4-di  ylindole              ethoxy-4-diethylaminophenyl                                                   )                                       ethylaminophenyl)                     (1,2-dimethylindol-3-yl)]-              (4-methylphenyl-                      methane                                 sulfonyl)]methane                                                    16   4.7 g                                                                             [(4-Methoxyphenyl)                                                                        1.68 g                                                                            1-Ethyl-                                                                             HCl  Ethanol                                                                             2.4 g                                                                             [(4-Methoxyphenyl)(2-                   (2-ethoxy-4-di- 2-methyl-             ethoxy-4-diethylamino-                  ethylaminophenyl)                                                                             indole                phenyl)(1-ethyl-2-meth-                 (4-methylphenyl-                      ylindol-3-yl)]methane                   sulfonyl)]methane                                                    17   9.1 g                                                                             [(4-Dimethylamino-                                                                        3.1 g                                                                             1,2-Di-                                                                              HCl  Ethanol                                                                             8.1 g                                                                             [(4-Dimethylaminophenyl)                phenyl)(1-ethyl-                                                                              methyl-               (1-ethyl-2-methylindol-                 2-methylindol-3-                                                                              indole                3-yl)(1,2-dimethylindol-                yl)(4-methylphen-                     3-yl)]methane                           ylsulfonyl)]meth-                                                             ane                                                                  18   9.1 g                                                                             [(4-Dimethylamino-                                                                        7.0 g                                                                             1- -n-Butyl-                                                                         HCl  Ethanol                                                                             9.3 g                                                                             [(4-Dimethylaminophenyl)                phenyl)(1-ethyl-                                                                              2-methyl-             (1-ethyl-2-methylindol-                 2-methylindole-3-                                                                             indole                3-yl)(1- -n-butyl-2-methyl-             yl)(4-methylphen-                     indol-3-yl)]methane                     ylsulfonyl)]meth-                                                             ane                                                                  19   4.1 g                                                                             [(2-Thienyl)(1-                                                                           1.2 g                                                                             Indole HCl  Acetone                                                                             1.98 g                                                                            [(2-Thienyl)(1-ethyl-2-                 ethyl-2-methyl-                       methylindol-3-yl)(indol-                indol-3-yl)(4-                        3-yl)]methane                           methylphenylsul-                                                              fonyl)]methane                                                       20   8.1 g                                                                             [(2-Thienyl)(1-                                                                           7.0 g                                                                             1- -n- HCl  Ethanol                                                                             10.5 g                                                                            [(2-Thienyl)(1-ethyl-                   ethyl-2-methyl- Butyl-2-              2-methylindol-3-yl)                     indol-3-yl)(4-  methyl-               (1- -n-butyl-2-methyl-                  methylphenylsul-                                                                              indole                indol-3-yl)]methane                     fonyl)]methane                                                       21   8.1 g                                                                             [(2-Thienyl)(1-                                                                           3.1 g                                                                             1,2-Di-                                                                              HCl  Ethanol                                                                             7.9 g                                                                             [(2-Thienyl)(1-ethyl-                   ethyl-2-methyl- methyl-               2-methylindol-3-yl)(1,2-                indol-3-yl)(4-  indole                dimethylindol-3-yl)]-                   methylphenylsul-                      methane                                 fonyl)]methane                                                       22   7.2 g                                                                             [(4-Methoxyphen-                                                                          3.2 g                                                                             1-Ethyl-                                                                             HCl  Ethanol                                                                             3.9 g                                                                             [(4-Methoxyphenyl)(4-                   yl)(4-dimethyl- 2-methyl-             dimethylaminophenyl)                    aminophenyl)(4- indole                (1-ethyl-2-methylindol-                 methylphenylsul-                      3-yl)]methane                           fonyl)]methane                                                       23   4.7 g                                                                             [(4-Methoxyphen-                                                                          2.0 g                                                                             2-Phenyl-                                                                            HCl  Ethanol                                                                             5.6 g                                                                             [(4-Methoxyphenyl)(4-                   yl)(4-dimethyl- indole                dimethylaminophenyl)                    aminophenyl)(4-                       (2-phenylindol-3-yl)]-                  methylphenylsul-                      methane                                 fonyl)]methane                                                       24   7.3 g                                                                             [(Phenyl)(4-di-                                                                           3.0 g                                                                             1,2-Di-                                                                              HCl  Ethanol                                                                             4.5 g                                                                             [(Phenyl)(4-dimethyl-                   methylaminophen-                                                                              methyl-               aminophenyl)(1,2-di-                    yl)(4-methylphen-                                                                             indole                methylindol-3-yl)]-                     ylsulfonyl)]meth-                     methane                                 ane                                                                  25   7.3 g                                                                             [(Phenyl(4-di-                                                                            3.55 g                                                                            1-Ethyl-                                                                             HCl  Ethanol                                                                             5.68 g                                                                            [(Phenyl)(4-dimethyl-                   methylaminophen-                                                                              2-methyl-             aminophenyl)(1-ethyl-                   yl)(4-methylphen-                                                                             indole                2-methylindol-3-yl)]-                   ylsulfonyl)]meth-                     methane                                 ane                                                                  26   8.8 g                                                                             [(Phenyl)(2-eth-                                                                          3.6 g                                                                             1-Ethyl-                                                                             HCl  Ethanol                                                                             10.0 g                                                                            [(Phenyl)(2-ethoxy-                     oxy-4-diethylamino-                                                                           2-methyl-             4-diethylaminophenyl)                   phenyl)(4-methyl-                                                                             indole                (1-ethyl-2-methylin-                    phenylsulfonyl)]-                     dol-3-yl)]methane                       methane                                                              27   9.4 g                                                                             [(2-Methoxyphen-                                                                          3.2 g                                                                             1-Ethyl-                                                                             HCl  Ethanol                                                                             5.3 g                                                                             [(2-Methoxyphenyl)(2-                   yl)(2-ethoxy-4- 2-methyl-             ethoxy-4-diethylamino-                  diethylaminophen-                                                                             indole                phenyl)(1-ethyl-2-meth-                 yl)(4-methylphen-                     ylindol-3-yl)]methane                   ylsulfonyl)]meth-                                                             ane                                                                  28   20.5 g                                                                            [(4-Nitrophenyl)                                                                          9.45 g                                                                            1-Ethyl-                                                                             HCl  Ethanol                                                                             7.31 g                                                                            [(4-Nitrophenyl)(4-                     (4-dimethylamino-                                                                             2-methyl-             dimethylaminophenyl)                    phenyl)(4-methyl-                                                                             indole                (1-ethyl-2-methylin-                    phenylsulfonyl)]-                     dol-3-yl)]methane                       methane                                                              29   8.38 g                                                                            [(4-Nitrophenyl)                                                                          3.25 g                                                                            1-Ethyl-                                                                             HCl  Ethanol                                                                             5.86 g                                                                            [(4-Nitrophenyl)(2-                     (2-ethoxy-4-di- 2-methyl-             ethoxy-4-diethylamino-                  ethylaminophenyl)                                                                             indole                phenyl)(1-ethyl-2-                      (4-methylphenyl-                      methylindol-3-yl)]-                     sulfonyl)]methane                     methane                        30   8.2 g                                                                             [(3-Nitrophenyl)                                                                          3.56 g                                                                            1-Ethyl-                                                                             HCl  Ethanol                                                                             1.89 g                                                                            [(3-Nitrophenyl)(4-                     (4-dimethylamino-                                                                             2-methyl-             dimethylaminophenyl)                    phenyl)(4-methyl-                                                                             indole                (1-ethyl-2-methylin-                    phenylsulfonyl)]-                     dol-3-yl)]methane                       methane                                                              31   9.6 g                                                                             [(3-Nitrophenyl)                                                                          3.56 g                                                                            1-Ethyl-                                                                             HCl  Ethanol                                                                             6.91 g                                                                            [(3-Nitrophenyl)(2-                     (2-ethoxy-4-di- 2-methyl-             ethoxy-4-diethyl-                       ethylaminophenyl)                                                                             indole                aminophenyl)(1-ethyl-                   (4-methylphenyl-                      2-methylindol-3-yl)]-                   sulfonyl)]methane                                                    32   4.6 g                                                                             [(4-Dimethylamino-                                                                        1.62 g                                                                            1-Ethyl-                                                                             HCl  Ethanol                                                                             0.15 g                                                                            [(4-Dimethylamino-                      phenyl)(9-juloli-                                                                             2-methyl-             phenyl)(9-julolidinyl)                  dinyl)(4-methyl-                                                                              indole                (1-ethyl-2-methylin-                    phenylsulfonyl)]-                     dol-3-yl)]methane                       methane                                                              33   11.2 g                                                                            [(4-Methoxyphenyl)                                                                        6.6 g                                                                             1- -n-Butyl-                                                                         HCl  Ethanol                                                                             2.3 g                                                                             [(4-Methoxyphenyl)                      (2-ethoxy-4-dieth-                                                                            2-methyl-             (2-ethoxy-4-diethyl-                    ylaminophenyl)(4-                                                                             indole                aminophenyl)(1- -n-but-                 methylphenylsul-                      yl-2-methylindol-3-                     fonyl)]methane                        yl)]methane                    34   17.9 g                                                                            [(3-Nitrophenyl)                                                                          10.1 g                                                                            1- -n-Butyl-                                                                         HCl  Ethanol                                                                             2.6 g                                                                             [(3-Nitrophenyl)(2-                     (2-ethoxy-4-di- 2-methyl-             ethoxy-4-diethylamino-                  ethylaminophenyl)                                                                             indole                phenyl)(1- -n-butyl-2-                  (4-methylphenyl-                      methylindol-3-yl)]-                     sulfonyl)]methane                     methane                        35   17.9 g                                                                            [(3-Nitrophenyl)                                                                          10.0 g                                                                            1-Allyl-                                                                             HCl  Ethanol                                                                             9.4 g                                                                             [(3-Nitrophenyl)(2-                     (2-ethoxy-4-di- 2-methyl-             ethoxy-4-diethylamino-                  ethylaminophenyl)                                                                             indole                phenyl)(1-allyl-2-                      (4-methylphenyl-                      methylindol-3-yl)]-                     sulfonyl)]methane                     methane                        36   7.8 g                                                                             [(4-Methoxyphen-                                                                          3.9 g                                                                             1-Methyl-                                                                            HCl  Ethanol                                                                             2.1 g                                                                             [(4-Methoxyphenyl)(4-                   yl)(4-dimethyl- indol-2-              dimethylaminophenyl)                    aminophenyl)(4- carboxylic            (1-methyl-2-carboxy-                    methylphenylsul-                                                                              acid                  indol-3-yl)]methane                     fonyl)]methane                                                       37   9.9 g                                                                             [(Phenyl)(4-di-                                                                           5.6 g                                                                             1- -n-Butyl-                                                                         HCl  Ethanol                                                                             2.45 g                                                                            [(Phenyl)(4-dimethyl-                   methylaminophen-                                                                              2-methyl-             aminophenyl)(1- -n-but-                 yl)(4-methylphen-                                                                             indole                yl-2-methylindol-3-                     ylsulfonyl)]-                         yl)]methane                             methane                                                              __________________________________________________________________________

                                      TABLE A                                     __________________________________________________________________________    PART II                                                                       Exam-                                                                         ple Formula                     Product                                                                              Melting                                                                              IR         Developed            No. No.  Substituents           Color  Point (°C.)                                                                   cm.sup.-1                                                                            NMR Color                __________________________________________________________________________    7   IV   R.sup.1 = R.sup.2 = R.sup.4 = R.sup.10 = R.sup.11                                                    Pale Tan                                                                             239-240                                                                              740(C--H;s)                                                                          Consis-                                                                           Grape on                      R.sup.3 = R.sup.5 = N(CH.sub.3).sub.2       tent                                                                              clay and                                                                      resin                8   IV   R.sup.1 = R.sup.2 = R.sup.4 = R.sup.9 = R.sup.11 = H; R.sup.3 =               R.sup.5 =              Pale Tan                                                                             148-151                                                                              740(C--H;s)                                                                          Consis-                                                                           Grape on                      N(CH.sub.3).sub.2 ; R.sup.10 = CH.sub.3     tent                                                                              clay and                                                                      resin                9   X    R.sup.1 =  R.sup.2 = R.sup.4 = R.sup.9'  = R.sup.11 = H;                      R.sup.3'  =            Brown  Tar    740(C--H;s)                                                                          Consis-                                                                           Violet on                     N(CH.sub.3).sub.2 ; R.sup.5 = N(C.sub.2 H.sub.5)(CH.sub.2                                                                 tent                                                                              clay and                      C.sub.6 H.sub.5); R.sup.10 = CH.sub.3           resin                10  X    R.sup.1 = R.sup.2 = R.sup.4 = R.sup.11 = H; R.sup.3'  =                                              Brown  Gum    740(C--H;s)                                                                          Consis-                                                                           Purple on                     N(CH.sub.3).sub.2 ; R.sup.5 = N(C.sub.2 H.sub.5)--                                                                        tent                                                                              clay and                      (CH.sub.2 C.sub.6 H.sub.5); R.sup.9'  = C.sub.2 H.sub.5 ;                                                                     resin                         R.sup.10 = CH.sub.3                                                  11  IV   R.sup.1 = R.sup.2 = R.sup.4 = R.sup.11 = H; R.sup.3  = R.sup.5                                       Pale Blue                                                                            177-184                                                                              740(C--H;s)                                                                          Consis-                                                                           Violet on                     N(CH.sub.3).sub.2 ; R.sup.9 = R.sup.10 = CH.sub.3                                                                         tent                                                                              clay and                                                                      resin                12  X    R.sup.1 = R.sup.2 = R.sup.4 = R.sup.11 = H; R.sup.3'  = R.sup.5               =                      Purple Gum    740(C--H;s)                                                                          Consis-                                                                           Violet on                     N(CH.sub.3).sub.2 ; R.sup.9 =  -n-C.sub.4 H.sub.9 ;                                                                       tent                                                                              clay and                      R.sup.10 = CH.sub.3                             resin                13  X    R.sup.1 = R.sup.2 = R.sup.4 = R.sup.11 = H; R.sup.3'  =                                              Pale Green-                                                                          58-60  730(C--H;s)                                                                          Consis-                                                                           Violet                        N(CH.sub.3).sub.2 ; R.sup.5 = N(C.sub.2 H.sub.5)--                                                   Gray                 tent                                                                              on clay                       (CH.sub.2 C.sub.6 H.sub.5 ); R.sup.9'  = R.sup.10 = CH.sub.3         14  X    R.sup.1 = R.sup.2 = R.sup.4 = R.sup.9'  = R.sup.10 = R.sup.11 =               H;                     Blue   Tar    742(C═H;s)                                                                       Consis-                                                                           Grape                         R.sup.3'  = N(CH.sub.3).sub.2 ; R.sup.5 = N(C.sub.2 H.sub.5)--                                                            tent                                                                              on clay                       (CHC.sub.6 H.sub.5)                                                  15  IV   R.sup.1 = R.sup.2 = R.sup.11 = H; R.sup.3 = OCH.sub.3 ;                                              Pale Green                                                                           Gummy Oil                                                                            730(C--H;s)                                                                          Consis-                                                                           Blue                          R.sup.4 = OC.sub.2 H.sub.5 ; R.sup.5 = N(C.sub.2 H.sub.5).sub.2               ;                                           tent                                                                              on clay                       R.sup.9 = R.sup.10 = CH.sub.3                                        16  X    R.sup.1 = R.sup.2 = R.sup.11 = H; R.sup.3 = OCH.sub.3 ;                                              Pale Green                                                                           Gum    735(C--H;s)                                                                          Consis-                                                                           Choco-                        R.sup.4 = OC.sub.2 H.sub.5 ; R.sup.5 = N(C.sub.2 H.sub.5).sub.2               ;                                           tent                                                                              late on                       R.sup.9'  = C.sub.2 H.sub.5 ; R.sup.10 = CH.sub.3                                                                             clay                                                                          Blue on                                                                       resin                17  V    R.sup.1 = R.sup.2 = R.sup.8 = R.sup.11 = H; R.sup.3                           = N(CH.sub.3).sub.2 ;  Pale Pink                                                                              167-170.5                                                                          743(C--H;s)                                                                          Consis-                                                                           Red                           R.sup.6 = C.sub.2 H.sub.5 ; R.sup.7 = R.sup.9 = R.sup.10 =                    CH.sub.3                                    tent                                                                              on clay              18  V    R.sup.1 = R.sup.2 = R.sup.8 = R.sup.11 = H; R.sup.3                           = N(CH.sub.3).sub.2 ;  Magenta                                                                              Gummy Oil                                                                            740(C--H;s)                                                                          --  Blue-Red                      R.sup.6 =  C.sub.2 H.sub.5 ; R.sup.7 = R.sup.10 = CH.sub.3 ;                  R.sup.9 =                                       on clay                        -n-C.sub.4 H.sub.9                                                  19  VII  R.sup.6 = C.sub.2 H.sub.5 ; R.sup.7 = CH.sub.3 ; R.sup.8 =                    R.sup.9 = R.sup.10 =   Brown  Tar    745(C--H;s)                                                                          --  Brown                         R.sup.11 = H                                    on clay              20  VII  R.sup.6 = C.sub.2 H.sub.5 ; R.sup.7 = R.sup.10 = CH.sub.3 ;                   R.sup.8 =              Brown  Gum    740(C--H;s)                                                                          --  Brown                         R.sup.11 = H; R.sup.9 =  -n-C.sub.4 H.sub.9     on clay              21  VII  R.sup.6 = C.sub.2 H.sub.5 ; R.sup.7 = R.sup.9 = R.sup.10 =                    CH.sub.3 ;             Pale Pink                                                                            167-170                                                                              743(C--H;s)                                                                          Consis-                                                                           Brown                         R.sup. 8 = R.sup.11 = H                     tent                                                                              on clay              22  X    R.sup.1 = R.sup.2 = R.sup.4 = R.sup.11 = H; R.sup.3'  = OCH.sub.3              ;                     White  145-146                                                                              742(C--H;s)                                                                          Consis-                                                                           Blue on                       R.sup.5 = N(CH.sub.3).sub.2 ; R.sup.9'  = C.sub.2 H.sub.5                                                                 tent                                                                              resin                         R.sup.10 = CH.sub.3                             Grape on                                                                      clay                 23  III  R.sup.1 = R.sup.2 = R.sup.4 = R.sup.9 = R.sup.11 = H; R.sup.3 =               OCH.sub.3 ;            Pale Pink                                                                            107-108                                                                              750(C--H;s)                                                                          Consis-                                                                           Blue on                       R.sup.5 = N(CH.sub.3).sub.2 ; R.sup.10 = C.sub.6 H.sub.5                                                                  tent                                                                              resin                                                                         Pink-                                                                         Brown                                                                         on clay              24  III  R.sup.1 = R.sup.2 = R.sup.3 = R.sup.4 = R.sup.11 = H; R.sup.5                                        Pale   149-150                                                                              745(C--H;s)                                                                          Consis-                                                                           Blue                          N(CH.sub.3).sub.2 ; R.sup.9 = R.sup.10 = CH.sub.3                                                    Purple               tent                                                                              on clay              25  X    R.sup.1 = R.sup.2 = R.sup.3'  = R.sup.4 = R.sup.11 = H; R.sup.5               =                      Cream  131-132                                                                              755(C--H;s)                                                                          Consis-                                                                           Blue                          N(CH.sub.3).sub.2 ; R.sup.9'  = C.sub.2 H.sub.5 ; R.sup.10 =                  CH.sub.3                                    tent                                                                              on clay              26  X    R.sup.1 = R.sup.2 = R.sup.3'  = H; R.sup.4 = OC.sub.2 H.sub.5 ;               R.sup.5 =              Light Tan                                                                            100-102                                                                              750(C--H;s)                                                                          Consis-                                                                           Blue on                       N(CH.sub.3).sub.2 ; R.sup.9'  = C.sub.2 H.sub.5 ; R.sup.10 =                  CH.sub.3                                    tent                                                                              resin                                                                         Green-                                                                        Brown                                                                         on clay              27  X    R.sup.1 = R.sup.2 = R.sup.11 = H; R.sup.3'  = OCH.sub.3 ;                     R.sup.4 =              White  112-113                                                                              750(C--H;s)                                                                          Consis-                                                                           Blue on                       OC.sub.2 H.sub.5 ; R.sup.5 = N(CH.sub.3).sub.2 ; R.sup.9'                                                                 tent                                                                              resin                         C.sub.2 H.sub.5 ; R.sup.10 = CH.sub.3           Tan on                                                                        clay                 28  X    R.sup.1 = R.sup.2 = R.sup.4 = R.sup.11 = H; R.sup.3'  = NO.sub.2              ;                      Yellow 168-170                                                                              755(C--H;s)                                                                          Consis-                                                                           Blue-                         R.sup.5 = N(CH.sub.3).sub.2 ; R.sup.9'  = C.sub.2 H.sub.5                                                                 tent                                                                              Green                         R.sup.10 = CH.sub.3                             on clay              29  X    R.sup.1 = R.sup.2 = R.sup.11 = H; R.sup.3'  = NO.sub.2 ; R.sup.4              =                      Yellow 116-118                                                                              760(C--H;s)                                                                          Consis-                                                                           Blue-                         OC.sub.2 H.sub.5 ; R.sup.5 = N(C.sub.2 H.sub.5); R.sup.9'                                                                 tent                                                                              Green                         C.sub.2 H.sub.5 ; R.sup.10 = CH.sub.3           on resin                                                                      Yellow-                                                                       Green                                                                         on clay              30  X    R.sup.1 = R.sup.3' R.sup.11 = H; R.sup.2 = NO.sub.2 ;                                                Yellow 138-139                                                                              755(C═H;s)                                                                       Consis-                                                                           Blue-                         R.sup.5 = N(CH.sub.3).sub.2 ; R.sup.9'  = C.sub.2 H.sub.5                                                                 tent                                                                              Green on                      R.sup.10 = CH.sub.3                             resin                                                                         Blue on                                                                       clay                 31  X    R.sup.1 = R.sup.3'  = R.sup.11 = H; R.sup.2 = NO.sub.2 ; R.sup.4              =                      Yellow 123-124                                                                              755(C--H;s)                                                                          Consis-                                                                           Blue on                       OC.sub.2 H.sub.5 ; R.sup.5 = N(C.sub.2 H.sub.5).sub.2 ; R.sup.9'               =                                          tent                                                                              resin                         C.sub.2 H.sub.5 ; R.sup.10 = CH.sub.3           Blue-                                                                         Green on                                                                      clay                 32  VI   R.sup.1 = R.sup.2 = R.sup.11 = H; R.sup.9 = C.sub.2 H.sub.5                                          Pale Blue                                                                            119-120                                                                              750(C--H;s)                                                                          Consis-                                                                           Blue on                       R.sup.10 = CH.sub.3                         tent                                                                              resin                                                                         Blue on                                                                       clay                 33  X    R.sup.1 = R.sup.2 = R.sup.11 = H; R.sup.3'  = OCH.sub.8 ;                     R.sup.4 =              Blue   Oil    750(C--H;s)                                                                          Consis-                                                                           Brown                         OC.sub.2 H.sub.5 ; R.sup.5 = N(C.sub.2 H.sub.5); R.sup.9'                                                                 tent                                                                              on clay                        -n-C.sub.4 H.sub.9 ; R.sup.10 = CH.sub.3       Gray on                                                                       resin                34  X    R.sup.1 = R.sup.3'  = R.sup.11 = H; R.sup.2 = NO.sub.2 ; R.sup.4              =                      Green  Oil    750(C--H;s)                                                                          Consis-                                                                           Gray-                         OC.sub.2 H.sub.5 ; R.sup.5 = N(C.sub.2 H.sub.5).sub.2 ; R.sup.9'               =                                          tent                                                                              Green                          -n-C.sub.4 H.sub.9 ; R.sup.10 = CH.sub.3       on clay                                                                       Blue-                                                                         Green                                                                         on resin             35  X    R.sup.1 = R.sup.3'  = R.sup.11 = H; R.sup.2 = NO.sub.2 ; R.sup.4              =                      Yellow 113-114                                                                              760(C--H;s)                                                                          Consis-                                                                           Green-                        OC.sub.2 H.sub.5 ; R.sup.5 = N(C.sub.2 H.sub.5).sub.2 ; R.sup.9'               =                                          tent                                                                              Gray                          CH.sub.2 CHCH.sub.2 ; R.sup.10 = CH.sub.3       on clay                                                                       Gray on                                                                       resin                36  XI   R.sup.1 = R.sup.2 = R.sup.4 = R.sup.11 = B.sup.11 = H; R.sup.3                                       White  195-197                                                                              760(C--H;s)                                                                          Consis-                                                                           Blue-                         OCH.sub.3 ; R.sup.5 = N(CH.sub.3).sub.2 ; R.sup.9                                                                         tent.sub.3                                                                        Purple                                                                        on clay                                                                       Red-                                                                          Purple                                                                        on resin             37  X    R.sup.1 = R.sup.2 = R.sup.3 = R.sup.4 = R.sup.11 = H; R.sup.5                                        Green  Tar    750(C--H;s)                                                                          Consis-                                                                           Blue-                         N(CH.sub.3).sub.2 ; R.sup.9'  =  -n-C.sub.4 H.sub.9 ;                                                                     tent                                                                              Purple                        R.sup.10 = CH.sub.3                             on clay                                                                       Blue on                                                                       resin                __________________________________________________________________________

EXAMPLE 38

With stirring a mixture of 325.0 ml of ethanol, 47.5 g of[(phenyl)(4-dimethylaminophenyl)(4-methylphenylsulfonyl)]methane, 25.0ml of 1-methylindol-2-carboxylic acid and 13.0 ml of concentratedhydrochloric acid was heated at reflux temperature for approximatelytwenty-two hours. The resultant solution was poured slowly intoapproximately 300.0 ml of cold water. The resulting suspension wasextracted with approximately 500.0 ml of toluene. The toluene layer wasseparated and washed consecutively with water and saturated sodiumchloride solution. The toluene layer was stirred for approximately onehour with decolorizing charcoal and filtered to remove the charcoal. Thetoluene was removed by evaporation leaving a dark blue-purple solid. Thesolid was suspended in ethanol, heated for approximately one hour andcooled to ambient temperature. The solid was collected by filtration,washed with isopropanol and dried to obtain 19.0 g of a mixture ofstarting methane and[(phenyl)(4-dimethylaminophenyl)(1-methyl-2-carboxyindol-3-yl)]methaneas determined by nuclear magnetic resonance spectroscopy. The resultingsolid was suspended in approximately 300.0 ml of toluene forapproximately one hour and the solid collected by filtration. Thetoluene-wet solid was reslurried in approximately 100.0 ml of toluene ata temperature of approximately 60° C. for approximately one hour. Aftercooling the slurry to approximately 40° C., the solid was collected byfiltration and dried to obtain 2.47 g of[(phenyl)(4-dimethylaminophenyl)(1-methyl-2-carboxyindol-3-yl)]methane(Formula XI: R¹ ═R² ═R³ ═R⁴ ═R¹¹ ═B"═H; R⁵ ═N(CH₃)₂ ; R⁹ ═CH₃), acream-colored solid which melted at 214°-215° C. A significant infraredmaximum appeared at 760 (C--H;s) cm⁻¹. The nuclear magnetic resonancespectrum was concordant with the assigned structure. A toluene solutionof the product spotted on an acidic clay-coated paper slowly developed amedium blue-colored image and spotted on a phenolic resin-coated paperslowly developed a dark blue-colored image.

EXAMPLE 39

In 50.0 ml of N,N-dimethylformamide, 5.0 g of[(phenyl)(4-dimethylaminophenyl)(1-methyl-2-carboxyindol-3-yl)]methaneprepared as described in Example 38 above, was dissolved with stirring.Slowly, 3.0 g of potassium carbonate was added to the solution andstirring was continued at approximately 45° C. for a period of fifteenminutes to effect solution. To the solution 5.0 ml of diethyl sulfatewas added and the resulting reaction mixture was maintained atapproximately 45° C. for approximately three hours. The resultingsolution was cooled to approximately 30° C. and slowly poured withstirring into 200.0 ml of a mixture of ice and water. The separatedsolid was collected by filtration, washed with water, and allowed to dryon the filter. The dried filter cake was reslurried twice in ethanol,each time for approximately one hour. The solid was collected byfiltration and dried to obtain 3.44 g of white solid. The solid wassuspended with stirring in approximately 200.0 ml of hot isopropanol forapproximately one hour. After cooling the slurry to ambient temperaturethe solid was collected by filtration and dried to obtain 1.11 g of thestarting methane. The filtrate was concentrated by evaporation and theseparated solid was collected by filtration and dried to obtain 1.27 gof[(phenyl)(4-dimethylaminophenyl)(1-methyl-2-ethoxycarbonylindol-3-yl)]methane(Formula XI: R¹ ═R² ═R³ ═R⁴ ═R¹¹ ═H; R⁵ ═N(CH₃)₂ ; R⁹ ═CH₃ ; B"═C₂ H₅),a white solid which melted at 145°-146° C. The infrared spectrum showeda significant maximum at 760 (C--H;s) cm⁻¹ and the nuclear magneticresonance spectrum was concordant with the assigned structure. A toluenesolution of the product spotted on an acidic clay-coated paper slowlydeveloped a blue-gray-colored image.

EXAMPLE 40

Following a procedure similar to that described above in Example 39, 1.5g of[(4-methoxyphenyl)(4-dimethylaminophenyl)(1-methyl-2-carboxyindol-3-yl)]methaneprepared in Example 36 above, 1.0 g of potassium carbonate and 1.0 ml ofdimethylsulfate were interacted in 25.0 ml of N,N-dimethylformamide atapproximately 45° C. for a period of two hours to obtain 0.94 g of[(4-methoxyphenyl)(4-dimethylaminophenyl)(1-methyl-2-methoxycarbonylindol-3-yl)]methane(Formula XI: R¹ ═R² ═R⁴ ═R¹¹ ═H; R⁵ ═N(CH₃)₂ ; R⁹ ═B"═CH₃), a whitesolid which melted at 157°-160° C. The infrared spectrum showed asignificant maximum at 755 (C--H;s) cm⁻¹ and the nuclear magneticresonance spectrum was consistent with the assigned structure. A toluenesolution of the product spotted on an acidic clay-coated paper slowlydeveloped a magenta-colored image and on a phenolic resin-coated paperslowly developed a pale purple-colored image.

EXAMPLE 41

With stirring 5.0 g of[(phenyl)(4-dimethylaminophenyl)(1-methyl-2-carboxyindol-3-yl)]methaneprepared in Example 36 above was dissolved in 50.0 ml ofN,N-dimethylformamide. Slowly, 3.0 g of potassium carbonate was added tothe solution and the resulting mixture was maintained at approximately45° C. for a period of fifteen minutes to effect solution. Withstirring, 4.9 g of 1-bromohexadecane was added to the solution. Thereaction solution was maintained at approximately 45° C. forapproximately four hours. The temperature of the solution was increasedto approximately 70° C. and an additional 4.9 g of 1-bromohexadecane wasadded. The resulting solution was maintained at reflux for approximatelyeighteen hours. After cooling to ambient temperature, the solution waspoured slowly with stirring into approximately 200.0 g of a mixture ofice and water. The resulting suspension of a tar-like solid in water wasextracted with toluene. After the toluene layer was separated from thewater layer, it was washed first with fresh water and then with watersaturated with sodium chloride. The separated toluene layer wasevaporated to dryness to obtain a yellow solid. The yellow solid wasreslurried in hexane. The solid was collected by filtration and dried toobtain 1.65 g of starting methane. The filtrate was evaporated to obtaina gold-colored oil. After sitting for approximately one week, thegold-colored oil had partially crystallized turning a tan-brown color.The tan-brown solid was stirred with hexane at ambient temperature andthe solid collected by filtration and dried to obtain 1.75 g of solid.This solid was pasted with hexane and the resulting paste was filtered,saving the filtrate. The filter cake was washed with a small amount ofhexane, the wash being saved, and the solid dried to obtain 0.12 g of[(phenyl)(4-dimethylaminophenyl)(1-methyl-2-hexadecanoxycarbonylindol-3-yl)]methane(Formula XI: R¹ ═R² ═R³ ═R⁴ ═R¹¹ ═H; R⁵ ═N(CH₃)₂ ; R⁹ ═CH₃ ; B"═C₁₆H₃₃), a white-colored solid which melted at 51°-52° C. A significantinfrared maximum appeared at 755 (C--H;s) cm⁻¹ and the nuclear magneticresonance spectrum was consistent with the assigned structure. A toluenesolution of the product spotted on an acid clay-coated paper slowlydeveloped a blue-purple-colored image. The solid which formed in thefiltrate from above was collected by filtration, discarding thefiltrate. The filter cake was washed with a small amount of hexane,saving the wash filtrate, and dried to obtain an additional 0.21 g of[(phenyl)(dimethylaminophenyl)(1-methyl-2-hexadecanoxycarbonylindol-3-yl)]methane.The two hexane washes were combined and evaporated to obtain anadditional 0.46 g of[(phenyl)(4-dimethylaminophenyl)(1-methyl-2-hexadecanoxycarbonylindol-3-yl)]methane.

EXAMPLE 42

Proceeding in a manner similar to that described in Example 2 above,20.5 g of[(phenyl)(4-dimethylaminophenyl)(4-methylphenylsulfonyl)]methane wasinteracted with 10.0 g of indole-2-carboxylic acid in the presence of5.6 ml of concentrated hydrochloric acid in 140.0 ml of ethanol toobtain 3.34 g of[(phenyl)(4-dimethylaminophenyl)(2-carboxyindol-3-yl)]methane (FormulaXI: R¹ ═R² ═R³ ═R⁴ ═R¹¹ ═B"═H; R⁵ ═N(CH₃)₂), a blue solid which meltedat 213°-215° C. The nuclear magnetic resonance spectrum was consistentwith the assigned structure. A toluene solution of the product spottedon an acid clay-coated paper slowly developed a purple-colored image andon a phenolic resin-coated paper slowly developed a dark blue-coloredimage.

EXAMPLE 43

In a manner similar to that described in Example 39 above, 3.34 g of[(phenyl)(4-dimethylaminophenyl)(2-carboxyindol-3-yl)]methane preparedin Example 42 above was interacted with 2.0 g of potassium carbonate and3.5 ml of diethyl sulfate in 33.4 ml of N,N-dimethylformamide atapproximately 45° C. for approximately three hours to obtain 2.47 g of[(phenyl)(4-dimethylaminophenyl)(2-ethoxycarbonylindol-3-yl)]methane(Formula XI: R¹ ═R² ═R³ ═R⁴ ═R⁹ ═R¹¹ ═H; R⁵ ═N(CH₃)₂ ; B"═C₂ H₅), a palepink-colored solid which melted at 72°-78° C. The infrared spectrum hada maximum which appeared at 760 (C--H;s) cm⁻¹ and the nuclear magneticresonance was consistent. A toluene solution of the product spotted onan acidic clay-coated paper slowly developed a pale pink-colored imageand on a phenolic resin-coated paper slowly developed a palepink-colored image.

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate [(2-R¹-3-R² -4-R³ -phenyl)(2-R⁴ -4-R⁵ -phenyl)(R-phenylsulfonyl))]methane andthe appropriate 1-R⁹ -2-R¹⁰ -5/6-R¹¹ -indole of Formula III, there willbe obtained the [(2-R¹ -3-R² -4-R³ -phenyl)(2-R⁴ -4-R⁵ -phenyl)(1-R⁹-2-R¹⁰ -5/6-R¹¹ -indole-3-yl)]methanes of Formula IV, Examples 44-60,presented in Table B hereinbelow.

                                      TABLE B                                     __________________________________________________________________________    METHANES OF FORMULA IV                                                        Example                                                                            R      R.sup.1                                                                              R.sup.2                                                                          R.sup.3                                                                              R.sup.4                                                                            R.sup.5                                                                             R.sup.9                                                                              R.sup.10                                                                          R.sup.11                   __________________________________________________________________________    44   4-CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                    H  N(CH.sub.3).sub.2                                                                    Cl   Cl    CH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.3                                                                          H                          45   4-Cl   H      H  N( -n-C.sub.3 H.sub.7).sub.2                                                         H    CH.sub.3 O                                                                           -n-C.sub.8 H.sub.17                                                                 CH.sub.3                                                                          H                          46   2-NO.sub.2                                                                            -n-C.sub.3 H.sub.7                                                                  H   -n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5 O                                                                  H     H      C.sub.2 H.sub.5                                                                   CH.sub.3                   47   H       -n-C.sub.4 H.sub.9 O                                                                H  N(C.sub.2 H.sub.5).sub.2                                                             CH.sub.3 O                                                                         CH.sub.3 O                                                                          CH.sub.2 C.sub.6 H.sub.5                                                             H   F                          48   4-CH.sub.3                                                                           C.sub.2 H.sub.5 O                                                                    H  Cl     H     .sub.-i-C.sub.3 H.sub.7                                                            CH.sub.3                                                                             H   NO.sub.2                   49   3,4-(Cl).sub.2                                                                       N(C.sub.2 H.sub.5).sub.2                                                             H  N(C.sub.2 H.sub.5).sub.2                                                             CH.sub.3 O                                                                         N(C.sub.2 H.sub.5).sub.2                                                            CH.sub.3                                                                             CH.sub.3                                                                          NO.sub.2                   50   4-I    Cl     H  N( .sub.-i-C.sub.3 H.sub.7).sub.2                                                    H    N(CH.sub.3)--                                                                       H      C.sub.2 H.sub.5                                                                   N                                                            (CH.sub.2 C.sub.6 H.sub.5)                  51   4-CH.sub.3 O                                                                         I      H  N( -n-C.sub.4 H.sub.9)--                                                             Br   H     4-ClC.sub.6 --                                                                       CH.sub.3                                                                          NO.sub.2                                         (CH.sub.2 C.sub.6 H.sub.5)                                                                      H.sub.4 CH.sub.2                      52   3-NO.sub.2                                                                           CH.sub.3                                                                             H  N(C.sub.2 H.sub.5).sub.2                                                              -n-C.sub.3 H.sub.7                                                                H     CH.sub.3                                                                             C.sub.2 H.sub.5                                                                   H                          53   H      H      H  N( -n-C.sub.3 H.sub.7)--                                                             CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                    .sub.-i-C.sub.3 H.sub.7                                                             H   H                                                (CH.sub.2 C.sub.6 H.sub.5)                              54   4-Br    -n-C.sub.3 H.sub.7 O                                                                H   -n-C.sub.3 H.sub.7 O                                                                CH.sub.3 O                                                                         H     H       .sub.-i-C.sub.3 H.sub.7                                                          H                          55   4-Cl--3NO.sub.2                                                                      H      H  N( .sub.-i-C.sub.4 H.sub.9)--                                                        H    C.sub.2 H.sub.5 O                                                                   CH.sub.3                                                                             H   Br,NO.sub.2                                      (CH.sub.2 C.sub.6 H.sub.5)                              56   4-CH.sub.3                                                                           N( -n-CH.sub.4 H.sub.9).sub.2                                                        H  N( -n-C.sub.4 H.sub.9).sub.2                                                         CH.sub.3 O                                                                         H     H      CH.sub.3                                                                          (CH.sub.3).sub.2           57   H      H      H  N( .sub.-i-C.sub.3 H.sub.7)--                                                        H    N(CH.sub.3).sub.2                                                                    .sub.-i-C.sub.4 H.sub.9                                                             CH.sub.3                                                                          H                                                (CH.sub.2 C.sub.6 H.sub.5)                              58   4-F    H      NO.sub.2                                                                         H      N(CH.sub.3).sub.2                                                                  N(CH.sub.3).sub.2                                                                   H      CH.sub.3                                                                          Br                         59   4-CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                    H  N(CH.sub.3).sub.2                                                                    H    CH.sub.3                                                                             -n-C.sub.6 H.sub.13                                                                 H   H                          60   4-CH.sub.3 --                                                                        CH.sub.3 O                                                                           H  CH.sub.3 O                                                                           H    N(C.sub.2 H.sub.5).sub.2                                                            2,5-(CH.sub.3).sub.2 --                                                              CH.sub.3                                                                          H                               CONH                               C.sub.6 H.sub.3 CH.sub.2              61   H      N(CH.sub. 3).sub.2                                                                   H  N(CH.sub.3).sub.2                                                                    CH.sub.3 O                                                                         N(C.sub.2 H.sub.5).sub.2                                                            H      COOH                                                                              5-Cl                       62   4-CH.sub.3                                                                           N(C.sub.2 H.sub.5).sub.2                                                             H  N(C.sub.2 H.sub.5).sub.2                                                             C.sub.2 H.sub.5 O                                                                  N(C.sub.2 H.sub.5).sub.2                                                            H      COOH                                                                              5-CH.sub.3 O               __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate [(2-R¹-3-R² -4-R³ -phenyl)(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)(R-phenylsulfonyl)]methane and the appropriate 1-R⁹ -2-R¹⁰-5/6-R¹¹ -indole of Formula III, there will be obtained the [(2-R¹ -3-R²-4-R³ -phenyl)(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)(1-R⁹ -2-R¹⁰ -5/6-R¹¹-indol-3-yl)]methanes of Formula V, Examples 63-74, presented in Table Chereinbelow.

                                      TABLE C                                     __________________________________________________________________________    METHANES OF FORMULA V                                                         Ex-                                                                           am-                                                                           ple                                                                              R      R.sup.1                                                                             R.sup.2                                                                          R.sup.3   R.sup.6                                                                              R.sup.7                                                                           R.sup.8                                                                              R.sup.9                                                                              R.sup.10                                                                          R.sup.11            __________________________________________________________________________    63 4-Br   CH.sub.3 O                                                                          H  N(CH.sub.3).sub.2                                                                       2-(C.sub.2 H.sub.5)--                                                                CH.sub.3                                                                          H      H      C.sub.2 H.sub.5                                                                   H                                                (C.sub.6 H.sub.5 CH.sub.2)                       64 2,4-(CH.sub.3).sub.2                                                                 Cl    H  N(CH.sub.3).sub.2                                                                       4-ClC.sub.6 H.sub.4 CH.sub.2                                                         CH.sub.3                                                                          5-NO.sub.2                                                                           CH.sub.3                                                                             C.sub.2 H.sub.5                                                                   H                   65 2-NO.sub.2                                                                           CH.sub.3                                                                            NO.sub.2                                                                         H          -n-C.sub.8 H.sub.17                                                                 CH.sub.3                                                                          H      CH.sub.3                                                                             H   5-Br,6-                                                                       NO.sub.2            66 3,4-(Cl).sub.2                                                                       H     H   .sub.-i-C.sub.3 H.sub.7                                                                CH.sub.3                                                                             H   5-Br--6-NO.sub.2                                                                     H      CH.sub.3                                                                          5,6-                                                                          (CH.sub.3).sub.                                                               2                   67 4-F    CH.sub.3 O                                                                          H  CH.sub.3 O                                                                              2-CH.sub.3 C.sub.6 --                                                                CH.sub.3                                                                          H       .sub.-i-C.sub.4 H.sub.9                                                             CH.sub.3                                                                          H                                                H.sub.4 CH.sub.2                                 68 4-CH.sub.3 O                                                                         CH.sub.3                                                                            H  N(CH.sub.3) (C.sub.6 --                                                                 H      C.sub.2 H.sub.5                                                                   6-CH.sub.3                                                                            -n-C.sub.6 H.sub.13                                                                 H   H                                      H.sub.5 CH.sub.2)                                          69 3-NO.sub.2                                                                           Br    H  NO.sub.2   .sub.-i-C.sub.4 H.sub.9                                                             CH.sub.3                                                                          H      2,5-(CH.sub.3).sub.2                                                                 CH.sub.3                                                                          H                                                                  C.sub.6 H.sub.3 CH.sub.2       70 4-CH.sub.3 CONH                                                                      H     H  C.sub.2 H.sub.5 O                                                                       1-(CH.sub.3)--                                                                       H   5-I    H      C.sub.2 H.sub.5                                                                   6-Cl                                             (C.sub.6 H.sub.12)                               71 4-Cl   H     H  N(CH.sub.3) (C.sub.6 H.sub.5 CH.sub.2)                                                  H       .sub.-i-C.sub.3 H.sub.7                                                          H      H      COOH                                                                              5-Cl                72 H      C.sub.2 H.sub.5 O                                                                   H  H         C.sub.2 H.sub.4                                                                      CH.sub.3                                                                          H      H      COOH                                                                              5-CH.sub.3 O        73 2,5-(CH.sub.3).sub.2                                                                 H     H  Cl         .sub.-i-C.sub.5 H.sub.11                                                            H   5-CH.sub.30                                                                          CH.sub.3                                                                             COOH                                                                              H                   74 H      N(CH.sub.3).sub.2                                                                   H  N(CH.sub.3).sub.2                                                                       CH.sub.3                                                                             C.sub.6 H.sub.5                                                                   H      H      H   5,6-                                                                          (CH.sub.3                                                                     O).sub.2            __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate [(2-R¹-3-R² -4-R³ -phenyl)(9-julolidinyl)(R-phenylsulfonyl)]methane and theappropriate 1-R⁹ -2-R¹⁰ -5/6-R¹¹ -indole, there will be obtained the[(2-R¹ -3-R² -4-R³ -phenyl)(9-julolidinyl)(1-R⁹ -2-R¹⁰ -5/6-R¹¹-indol-3-yl)]methanes of Formula VI, Examples 75-84, presented in TableD hereinbelow.

                                      TABLE D                                     __________________________________________________________________________    METHANES OF FORMULA VI                                                        Example                                                                            R      R.sup.1                                                                            R.sup.2                                                                          R.sup.3    R.sup.9                                                                              R.sup.10                                                                          R.sup.11                            __________________________________________________________________________    75   2,5-(CH.sub.3).sub.2                                                                 Cl   H  N(CH.sub.3).sub.2                                                                        H      C.sub.6 H.sub.5                                                                   5,6-(Cl).sub.2                      76   H      H    H  Cl          .sub.-i-C.sub.5 H.sub.11                                                            H   H                                   77   4-Cl   N(CH.sub.3).sub.2                                                                  H  N(CH.sub.3).sub.2                                                                        2-FC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                          H                                   78   2-NO.sub.2                                                                           C.sub.2 H.sub.5 O                                                                  H  N(CH.sub.3).sub.2                                                                        3-(2-CH.sub.3)--1-                                                                   CH.sub.3                                                                          H                                                                  C.sub.3 H.sub.5                                79   3,4-(Cl).sub.2                                                                       CH.sub.3                                                                           H  N(CH.sub.3).sub.2                                                                        H      H   5,6-(CH.sub.3 O).sub.2              80   H      H    H  N(C.sub.2 H.sub.5) (C.sub.6 H.sub.5 CH.sub.2)                                            H      COOH                                                                              H                                   81   4-CH.sub.3 CONH                                                                       -n-C.sub.4 H.sub.9 O                                                              H  N( -n-C.sub.4 H.sub.9).sub.2                                                             H      COOH                                                                              Cl                                  82   H      H    NO.sub.2                                                                         H          CH.sub.3                                                                             COOH                                                                              H                                   83   4-Br   CH.sub.3                                                                           H  NO.sub. 2  H      COOH                                                                              5-CH.sub.3 O                        84   4-CH.sub.3                                                                           Br   H  Br          -n-C.sub.12 H.sub.25                                                                CH.sub.3                                                                          H                                   __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate[(2-thienyl)(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)(R-phenylsulfonyl)]methaneand the appropriate 1-R⁹ -2-R¹⁰ -5/6-R¹¹ -indole, there will be obtainedthe [(2-thienyl)(-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)(1-R⁹ -2-R¹⁰ -5/6-R¹¹-indol-3-yl)]methanes of Formula VII, Examples 85-95, presented in TableE hereinbelow.

                                      TABLE E                                     __________________________________________________________________________    METHANES OF FORMULA VII                                                       Example                                                                            R      R.sup.6                                                                            R.sup.7                                                                          R.sup.8                                                                            R.sup.9                                                                              R.sup.10                                                                          R.sup.11                                  __________________________________________________________________________    85   2-NO.sub.2                                                                           CH.sub.3                                                                           CH.sub.3                                                                         H    C.sub.2 H.sub.4                                                                      CH.sub.3                                                                          H                                         86   4-Br   H    H  5-CH.sub.3 O                                                                       CH.sub.3                                                                             CH.sub.3                                                                          6-NO.sub.2                                87   4-CH.sub.3 CONH                                                                      H    C.sub.6 H.sub.5                                                                  H     .sub.-i-C.sub.4 H.sub.9                                                             CH.sub.3                                                                          H                                         88   2,4-(CH.sub.3).sub.2                                                                 H    C.sub.2 H.sub.5                                                                  H    H      COOH                                                                              5-CH.sub.3 O                              89   H      C.sub.2 H.sub.4                                                                    CH.sub.3                                                                         H     -n-C.sub.10 H.sub.13                                                                CH.sub.3                                                                          H                                         90   4-C.sub.2 H.sub.5                                                                    H    CH.sub.3                                                                         6-Br H      CH.sub.3                                                                          6-Br                                      91   4-NO.sub.2                                                                            .sub.-i-C.sub.3 H.sub.7                                                           H  H    C.sub.6 H.sub.5 CH.sub.2                                                             H   6-F                                       92   4-Br   H    C.sub.2 H.sub.5                                                                  6-CH.sub.3                                                                         H      C.sub.2 H.sub.5                                                                   H                                         93   4-CH.sub.3 O                                                                         C.sub.6 H.sub.5 CH.sub.2                                                           CH.sub.3                                                                         H    H      COOH                                                                              H                                         94   H      C.sub.2 H.sub.5                                                                    CH.sub.3                                                                         H    H      C.sub.2 H.sub.5                                                                   6-CH.sub.3                                95   4-C.sub.2 H.sub.5 O                                                                   -n-C.sub.8 H.sub.17                                                               CH.sub.3                                                                         H    4-BrC.sub.6 H.sub.4 CH.sub.2                                                          .sub.-i-C.sub.3 H.sub.7                                                          H                                         __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in foregoing Example 39 but employing the appropriate[(X)(Y)(1-R⁹ -2-carboxy-5/6-R¹¹ -indol-3-yl)]methane and dimethylsulfate, diethyl sulfate or the appropriate B'-halogen, there will beobtained the [(X)(Y)(1-R⁹ -2-B'O-carbonyl-5/6-R¹¹ -indol-3-yl)]methanesof Formula VIII, Examples 96-106, presented in Table F hereinbelow.

                                      TABLE F                                     __________________________________________________________________________    METHANES OF FORMULA VIII                                                      Example                                                                            X             Y              R.sup.9                                                                          R.sup.11                                                                           B'                                  __________________________________________________________________________     96  2,4-[(CH.sub.3).sub.2 N].sub.2 C.sub.6 H.sub.3                                              2-CH.sub.3 O--4-(C.sub.2 H.sub.5).sub.2 NC.sub.6                              H.sub.3        H  5-Cl  -n-C.sub.4 H.sub.9                  97  2,4-[(CH.sub.3).sub.2 N].sub.2 C.sub.6 H.sub.3                                              2-C.sub.2 H.sub.5 O--4-(C.sub.2 H.sub.5).sub.2                                NC.sub.6 H.sub.3                                                                             H  5-CH.sub.3 O                                                                        -n-C.sub.6 H.sub.11                 98  4-(CH.sub.3) (C.sub.6 H.sub.5 CH.sub.2)NC.sub.6 H.sub.3                                     1- .sub.-i-C.sub.3 H.sub.7 --indol-3-yl                                                      H  5-Cl C.sub.6 H.sub.5 CH.sub.2             99  2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                          1-C.sub.2 H.sub.4 --2-CH.sub.3 --indol-3-yl                                                  CH.sub.3                                                                         H     -n-C.sub.6 H.sub.13                100  4-ClC.sub.6 H.sub.4                                                                         1- .sub.-i-C.sub.5 H.sub.11 --5-CH.sub.3 O--indol-3-yl                                       CH.sub.3                                                                         H    4-ClC.sub.6 H.sub.4 CH.sub.2        101  4-(C.sub.2 H.sub.5) (C.sub.6 H.sub.5 CH.sub.2)NC.sub.6 H.sub.3                              9-julolidinyl  H  H     -n-C.sub.16 H.sub.33               102  2- -n-C.sub.4 H.sub.9 OC.sub.6 H.sub.4                                                      9-julolidinyl  H  5-Cl 4-CH.sub.3 C.sub.6 H.sub.4                                                    CH.sub.2                            103  3-NO.sub.2 C.sub.6 H.sub.4                                                                  9-julolidinyl  H  H     .sub.-i-C.sub.3 H.sub.7            104  2-CH.sub.3 --4-NO.sub.2 C.sub.6 H.sub.3                                                     9-julolidinyl  H  5-CH.sub.3 O                                                                        .sub.-i-C.sub.8 H.sub.17           105  2-thienyl     2,4-[(C.sub.2 H.sub.5).sub.2 N].sub.2 C.sub.6 H.sub.3                                        H  5-CH.sub.3 O                                                                       4-BrC.sub.6 H.sub.4 CH.sub.2        106  2-thienyl     2,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                         H  H    C.sub.4 H.sub.7                     __________________________________________________________________________

EXAMPLE 107

The use of the compounds of Formulas I, X, XI, XII and XIII described inExamples 1 through 106, as color-forming components inpressure-sensitive microencapsulated copying systems is illustrated withreference to the product of Example 1.

A. A mixture of 60.0 g of i-propylbiphenyl and 1.46 g of[bis(4-dimethylaminophenyl)(1-ethyl-2-methylindol-3-yl)]methane,prepared as described above in Example 1 was heated to 95° C. until aclear solution was formed and then cooled to approximately 50° C. Asecond solution of 5.0 g of carboxymethylcellulose dissolved in 200.0 mlof distilled water was prepared. A third solution containing 15.0 g of275 Bloom gelatin dissolved in 120.0 ml of distilled water was heated atapproximately 50° C. for about one hour.

B. Two solutions, the first containing the product and thei-propylbiphenyl, and the second containing the carboxymethylcelluloseand the water were mixed and emulsified using a variable speed one-halfhorsepower Eppenbach Homo-Mixer (Gifford-Wood Co., Hudson, N.Y.) forapproximately fifteen minutes at an applied voltage of 30 volts untilthe particle size of the suspended emulsion was approximately 5 micronsat approximately 50° C. While maintaining the rapid agitation, the thirdsolution containing the gelatin and water was added and the pH adjustedto 6.5 with the addition of 10 percent aqueous sodium hydroxide. Slowly670.0 ml of distilled water at approximately 50° C. was added and the pHwas adjusted to 4.5 by the addition of 10 percent aqueous acetic acid.After five minutes of rapid agitation the mixture was cooled toapproximately 15° C. by means of an external ice-water bath and 10.0 mlof a twenty-five percent glutaraldehyde solution was added dropwise andagitation continued for 15 minutes. At this time, the EppenbachHomo-Mixer was replaced with a conventional blade type laboratoryagitator and the suspension was stirred overnight. The suspension wasadjusted to 1120.0 g with the addition of distilled water.

C. The stock microcapsule suspension prepared in part B above was coatedon paper sheets to a thickness of approximately 0.0015 inch and thecoated paper air dried. The paper thus coated with the microencapsulatedcolorless precursor was assembled as the top sheet in a manifold systemby positioning the coated side in contact with the coated side of acommercially-available receiving sheet coated with a color developer ofthe electron-accepting type. More specifically, papers coated with aphenolic resin and with an acidic clay were employed in this test. Animage was then drawn with a stylus on the top sheet bearing themicroencapsulated colorless precursor on its reverse side causing theeffected microcapsules to rupture thus allowing the solution of thecolorless precursor held by said microcapsules to flow into contact withthe color-developing substance on the receiving sheet whereupon aviolet-colored image slowly formed. The developed image exhibited goodtinctorial strength and excellent xerographic copiabilitycharacteristics.

When evaluated in a duplicating system prepared and tested as describedabove, the product of Example 3,[(4-dimethylaminophenyl)(1-ethyl-2-methylindolyl)(2-methylindol-3-yl)]methane,produced a blue-red-colored image; and the product of Example 5,[(2-thienyl)(1-ethyl-2-methylindol-3-yl)(2-methylindol-3-yl)]methane,produced a brown-colored image.

EXAMPLE 108

Proceeding in a manner similar to that described in Example 107 above, amixture of 0.73 g of[(4-nitrophenyl)(2-ethoxy-4-diethylaminophenyl)(1-ethyl-2-methylindol-3-yl)]methaneprepared as described in Example 29 above and 0.73 g of2-anilino-3-methyl-6-diethylaminofluoran were encapsulated. The capsuleswere coated on paper and the paper was assembled into a manifold system.An image was then drawn on the top sheet bearing the microencapsulatedcolorless precursor on its reverse side causing the effectedmicrocapsules to rupture thus allowing the solution of the mixture ofcolorless precursor held be said microcapsules to flow into contact withthe color developing substance on the receiving sheet whereupon ared-black-colored image developed on the acidic clay-coated paper and agreen-black-colored image developed on the resin coated paper. After 64hours of exposure to air, the image on the acidic clay-coated paper hadchanged to a red-brown-colored image and the image on the resin-coatedpaper had changed to a gray-black-colored image.

EXAMPLE 109

The utility of the compounds of Formulas I, X, XI, XII and XIII whosepreparations are described in the foregoing examples as color-formingcomponents in thermal marking systems is illustrated by theincorporation and testing of the compound of Example 1,[bis(4-dimethylaminophenyl)(1-ethyl-2-methylindol-3-yl)]methane in athermal-sensitive marking paper. The test paper was prepared by aprocedure similar to that described in U.S. Pat. No. 3,539,375.

A. A mixture of 2.0 g of[bis(4-dimethylaminophenyl)(1-ethyl-2-methylindol-3-yl)]methane, 8.6 gof a ten percent aqueous solution of polyvinyl alcohol (approximately 99percent hydrolyzed), 3.7 g of water and 31.6 g of 1/16 inch diameterzirconium grinding beads were charged into a container which was placedin a mechanical shaker. Shaking was effected for one hour. The zirconiumbeads were then removed by straining the mixture through a No. 40 sieve.

B. Similarly, a mixture of 9.8 g of 4,4'-isopropylidine diphenol(Bisphenol A), 42.0 g of a ten percent aqueous polyvinyl alcoholsolution (approximately 99 percent hydrolyzed), 18.2 g of water and221.2 g of 1/16 inch diameter zirconium grinding beads was charged intoa container which was placed in a mechanical shaker. After shaking waseffected for one hour, the zirconium beads were removed by strainingthrough a No. 40 sieve.

C. A coating composition was prepared by mixing 2.1 g of the slurry frompart A and 47.9 g of the slurry from part B. The mixture was thenuniformly coated on sheets of paper at a thickness of approximately0.0015 inch and the coated sheets air dried. The coated paper was testedby tracing a design on the coated side of the paper placed on a smoothflat surface with a stylus heated to approximately 125° C. Aviolet-colored image corresponding to the traced design promptlydeveloped.

When evaluated in thermal marking paper prepared and tested as describedabove, the product of Example 5,[(2-thienyl)(1-ethyl-2-methyl-3-indolyl)(2-methylindol-3-yl)]methane,produced a light brown-orange-colored image at approximately 125° C.;and the product of Example 4,[(1-ethyl-2-methylindol-3-yl)(4-dimethylaminophenyl)(indol-3-yl)]methane,produced a rose-pink-colored image at approximately 100° C.

EXAMPLE 110

The utility of the compounds of Formulas I, X, XI, XII and XIII whosepreparations are described in the foregoing examples as color-formingcomponents in thermal marking systems is illustrated by theincorporation and testing of the compound[(4-methoxyphenyl)-bis(1-ethyl-2-methylindol-3-yl)]methane in athermal-sensitive marking paper. The test paper was prepared by aprocedure similar to that described in U.S. Pat. No. 3,447,944.

A. A mixture of 7.60 g of oxidized starch dispersed in 30.0 ml ofdistilled water was heated at a temperature in the range of 90°-93° C.for approximately twenty minutes to effect solution. The solution wascooled to ambient temperature and set aside.

B. Similarly, a mixture of 15.0 g of disodium phosphate, 50.0 ml ofdistilled water and 2.8 g of sodium hydroxide was heated with stirringto effect complete solution. The resulting solution was maintained at atemperature in the range of 40°-50° C.

C. A mixture of 4.0 g of[(4-methoxyphenyl)-bis(1-ethyl-2-methylindol-3-yl)]methane, 3.3 g of thestarch solution from part A above, 16.0 ml of distilled water, 4.1 g ofthe disodium phosphate solution from part B above and 20.0 g of glassshot was charged into a container which was placed onto a roller mill.Rolling was effected for approximately thirty minutes. The container wasplaced then in a mechanical shaker and shaking was effected forapproximately thirty minutes. The glass beads were removed by strainingthe mixture through cotton gauze.

D. To a solution of 10.8 ml of distilled water, 14.2 g of disodiumphosphate solution from part B above and 16.3 g of of starch solutionfrom part A above, there was added slowly with stirring a mixture of 2.6g of benzoyl peroxide and 5.6 g of oxidized starch. The resultingmixture was stirred vigorously using a Hamilton Beach No. 30 drinkmastermixer for approximately thirty minutes.

E. With stirring 11.3 g of the dispersion containing the dyestuff frompart C above was combined with 20.4 g of the dispersion containing thebenzoyl peroxide from part D above. The mixture was then uniformlycoated on sheets of paper at a thickness of approximately 0.0015 inchand the coated sheets were air dried. The coated paper was tested bytracing a design on the coated side of the paper placed on a smooth flatsurface with two styli, one heated to approximately 100° C. and thesecond heated to approximately 125° C. A rose-colored imagecorresponding to the traced design at 100° C. promptly developed and abrick red-colored image corresponding to the traced design at 125° C.promptly developed.

A series of six solutions were prepared by dissolving varying amounts ofthe compounds of Formulas I, X, XI, XII and XIII or mixtures thereofwith other known colorless precursors in 50.0 ml of toluene. Thecolorless precursor solutions were then streaked on both an acidicclay-coated paper and an acidic resin-coated paper and the streakedpaper exposed to the air for a period of twenty-four hours. Thefollowing table describes in column 1, the example number; in column 2,the weight and chemical name of the colorless precursor(s); in column 3,the source of the colorless precursor; and in column 4, the color of thedeveloped image after twenty-four hours of air exposure on both acidicclay- and resin-coated paper.

                                      TABLE G                                     __________________________________________________________________________    Example                                                                            Amount and Name    Source of  Color of Developed Image                   No.  of Colorless Precursor(s)                                                                        Colorless Precursors                                                                     Clay Paper                                                                            Resin Paper                        __________________________________________________________________________    111  1.0 g                                                                            [(4-Methoxyphenyl) (2-ethoxy-4-                                                               Example 27 red-brown                                                                             gray                                       diethylaminophenyl) (1-ethyl-2-                                               methylindol-3-yl)]methane                                             112  1.5 g                                                                            2-Anilino-3-methyl-6-diethyl-                                                                 *          red-brown                                                                             red-black                                  aminofluoran                                                          113  1.0 g                                                                            [(4-Methoxyphenyl) (2-ethoxy-4-                                                               Example 27 dark red-brown                                                                        dark red-                                  diethylaminophenyl) (1-ethyl-2-    brown                                      methylindol-3-yl)]methane                                                  1.5 g                                                                            2-Anilino-3-methyl-6-diethyl-                                                                 *                                                             aminofluoran                                                          114  1.0 g                                                                            [(4-Methoxyphenyl) (2-ethoxy-4-                                                               Example 27 dark red                                                                              black                                      diethylaminophenyl) (1-ethyl-2-                                               methylindol-3-yl)]methane                                                  1.5 g                                                                            2-N--Benzylamino-3-methyl-6-                                                                  **                                                            diethylamino-5'/6'-ethoxy-                                                    carbonylfluoran                                                       115  1.0 g                                                                            [(4-Methoxyphenyl) (2-ethoxy-                                                                 Example 27 dark red                                                                              dark red-                                  4-diethylaminophenyl) (1-ethyl-    black                                      2-methylindol-3-yl)]methane                                                0.5 g                                                                            3,3-Bis(1- -n-butyl-2-methyl-                                                                 ***                                                           indol-3-yl)phthalide                                                       1.5 g                                                                            2-N--Benzylamino-3-methyl-6-                                                                  **                                                            diethylamino-5'/6'-ethoxy-                                                    carbonylfluoran                                                       116  1.0 g                                                                            [(Phenyl) (4-dimethylamino-                                                                   Example 24 red-black                                                                             black                                      phenyl) (1,2-dimethylindol-3-                                                 yl)]methane                                                                1.5 g                                                                            2-Anilino-3-methyl-6-diethyl-                                                                 *                                                             aminofluoran                                                          __________________________________________________________________________     *U.S. Pat. No. 3,681,370                                                      **U.S. Pat. No. 4,274,660                                                     ***U.S. Pat. No. 3,509,173                                               

We claim:
 1. A [(2--R¹ --3--R² --4--R³ --phenyl)(2--R⁴ --4--R⁵-phenyl)(1--R⁹ --2B"O--5/6--R¹¹ -indol-3-yl)]methane having the formula##STR24## wherein: R¹ represents hydrogen, C₁ to C₃ alkyl, non-tertiaryC₁ to C₄ alkoxy, halo or dialkylamino in which alkyl is non-tertiary C₁to C₄ alkyl;R² represents hydrogen or nitro; R³ represents hydrogen, C₁to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo, dialkylamino orN-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄ alkyl andbenzyl may be substituted in the benzene ring by one or two of halo orC₁ to C₃ alkyl; R⁴ represents hydrogen, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy, halo or dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl; R⁵ represents dialkylamino orN-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄ alkyl andbenzyl may be substituted in the benzene ring by one or two of halo orC₁ to C₃ alkyl; R⁹ represents hydrogen, C₁ to C₁₈ alkyl, C₂ to C₄alkenyl, benzyl and benzyl substituted in the benzene ring by one or twoof halo; R¹¹ represents one or two of hydrogen, C₁ to C₃ alkyl, C₁ to C₃alkoxy, halo or nitro; B" represents hydrogen, C₂ to C₈ alkenyl, benzylor benzyl substituted in the benzene ring by one or two of halo or C₁ toC₃ alkyl. 2.[(Phenyl)(4-dimethylaminophenyl)(2-carboxyindol-3-yl)]methane accordingto claim 1.